Safened compositions comprising pyridine carboxylate herbicides and cloquintocet

ABSTRACT

Disclosed herein are safened compositions comprising (a) a pyridine carboxylate herbicide or an agriculturally acceptable N-oxide, salt or ester thereof and (b) a quinolinoxyacetate safener or agriculturally acceptable salt or ester thereof. Also disclosed herein are methods of controlling undesirable vegetation, comprising applying to vegetation or an area adjacent the vegetation or applying in soil or water to control the emergence or growth of vegetation (a) a pyridine carboxylate herbicide or an agriculturally acceptable N-oxide, salt or ester thereof and (b) a quinolinoxyacetate safener or agriculturally acceptable salt or ester thereof.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of priority of U.S. Provisional Application No. 62/756,163, filed Nov. 6, 2018, which is incorporated by reference herein in its entirety.

FIELD OF THE DISCLOSURE

The disclosure includes safened compositions comprising a pyridine carboxylate herbicide and the safener cloquintocet, as well as methods of controlling undesirable vegetation using the same.

BACKGROUND

Many recurring problems in agriculture involve controlling the growth of undesirable vegetation that can, for instance, negatively affect the growth of desirable vegetation. To help control undesirable vegetation, researchers have produced a variety of chemicals and chemical formulations effective in controlling such unwanted growth.

In some cases, although a herbicide may be effective in controlling undesirable vegetation, it may also have a phytotoxic effect on a crop and cause injury or even kill the crop. Accordingly, there exists a need for new herbicides combined with safeners that limit the phytotoxicity of the herbicidal active ingredient with desired crops.

SUMMARY

Disclosed herein are safened compositions that may be used as a herbicides, for example, in crops. The safened compositions may contain (a) a pyridine carboxylate herbicide or agriculturally acceptable N-oxide, salt, or ester thereof and (b) the quinolinoxyacetate safener cloquintocet or an agriculturally acceptable salt or ester thereof. The weight ratio of (a) to (b) can be from 1:5 to 65:1 (e.g., from 1:5 to 5:1, or from 1:2 to 2:1).

In some aspects, the safened composition comprises (a) a pyridine carboxylate herbicide defined by Formula (I):

wherein:

-   -   R¹ is cyanomethyl or propargyl;     -   R² and R^(2′) are independently hydrogen, C₁-C₆ alkyl, formyl,         alkoxycarbonyl, or acyl;     -   R³, R^(3′), R^(3″), and R^(3′″) are independently hydrogen,         halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₃ alkoxy, or C₁-C₃         haloalkoxy;     -   or an agriculturally acceptable N-oxide, salt, or ester thereof;         and         (b) a safener comprising cloquintocet, or an agriculturally         acceptable salt or ester thereof.

In some aspects, the safened composition comprises:

(a) the pyridine carboxylate herbicide compound cyanomethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, referred to hereinafter as Compound A:

or an agriculturally acceptable N-oxide, salt, or ester thereof; and (b) a safener comprising cloquintocet or an agriculturally acceptable salt or ester thereof.

In some aspects, the safened composition comprises:

(a) the pyridine carboxylate herbicide compound propargyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, referred to hereinafter as Compound B:

or an agriculturally acceptable N-oxide, salt, or ester thereof; and (b) a safener comprising cloquintocet or an agriculturally acceptable salt or ester thereof.

In some aspects, the composition can further comprise an agriculturally acceptable adjuvant or carrier, an additional pesticide, or combinations thereof. In some aspects, the only active ingredients in the composition are (a) and (b).

Also disclosed herein are methods of controlling undesirable vegetation, comprising applying to vegetation, to an area adjacent the vegetation, or to soil or water to control the emergence or growth of vegetation, a safened composition comprising: (a) a pyridine carboxylate herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof; and (b) a safener comprising cloquintocet or an agriculturally acceptable salt or ester thereof. In some aspects, (a) and (b) are applied simultaneously. In some aspects, (a) and (b) are applied sequentially. In some aspects, (a) and (b) are applied pre-emergence of the undesirable vegetation. In some aspects, (a) and (b) are applied post-emergence of the undesirable vegetation. In some aspects, (a) is applied pre-emergently or post-emergently to the undesirable vegetation, and (b) is applied as seed treatment to the crop. In some aspects, the undesirable vegetation is in cereals. In some aspects, the undesirable vegetation is in maize, wheat, barley, rice, sorghum, millet, or oats. In some aspects, the undesirable vegetation is in broadleaf crops. In some aspects, the undesirable vegetation is in canola, flax, sunflower, soy, or cotton.

In some cases, the pyridine carboxylate herbicide (a) can be applied in an amount of from 0.1 gram active ingredient per hectare (g ai/ha) to 300 g ai/ha (e.g., from 30 g ai/ha to 40 g ai/ha). In some cases, the cloquintocet (b) can be applied in an amount of from 1 g ai/ha to 300 g ai/ha (e.g., from 30 g ai/ha to 40 g ai/ha). In some cases, (a) and (b) can be applied in a weight ratio of from 1:5 to 65:1 (e.g., from 1:5 to 5:1, or from 1:2 to 2:1).

The description below sets forth details of one or more aspect of the present disclosure. Other features, objects, and advantages will be apparent from the description and from the claims.

DETAILED DESCRIPTION

The present disclosure includes safened compositions comprising: (a) a pyridine carboxylate herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof and (b) the quinolinoxyacetate safener cloquintocet or an agriculturally acceptable salt or ester thereof. The present disclosure also includes methods for controlling undesirable vegetation. In some aspects, the undesirable vegetation is in cereals. In some aspects, the undesirable vegetation is in maize, wheat, barley, rice, sorghum, millet, or oats. In some aspects, the undesirable vegetation is in broadleaf crops. In some aspects, the undesirable vegetation is in canola, flax, sunflower, soy, or cotton.

I. Definitions

Terms used herein will have their customary meaning in the art unless specified otherwise. The singular forms “a,” and “the” include plural references unless stated otherwise. The present disclosure also contemplates other embodiments “comprising,” “consisting of” and “consisting essentially of,” the embodiments or elements presented herein, whether explicitly set forth or not. To the extent that the term “or” is employed (e.g., A or B) it is intended to mean “A or B or both.” If this disclosure intends to indicate “only A or B but not both” then the term “only A or B but not both” will be employed. Thus, use of the term “or” herein is the inclusive and not the exclusive use.

The chemical moieties mentioned when defining variable positions within the general formulae described herein (e.g., the term “alkyl”) are collective terms for the individual substituents encompassed by the chemical moiety. The prefix C_(n)-C_(m) preceding a group or moiety indicates, in each case, the possible number of carbon atoms in the group or moiety that follows.

As used herein, the terms “herbicide” and “herbicidal active ingredient” may be understood to include an active ingredient that kills, controls, or otherwise adversely modifies the growth of vegetation, particularly undesirable vegetation such as weed species, when applied in an appropriate amount.

As used herein, the term “herbicidal effect” may be understood to include an adversely modifying effect of an active ingredient on vegetation, including, for example, a deviation from natural growth or development, killing, regulation, desiccation, growth inhibition, growth reduction, and retardation. The term “herbicidal activity” refers generally to herbicidal effects of an active ingredient.

As used herein, “applying” a herbicide or herbicidal composition refers to delivering it directly to the targeted vegetation or to the locus thereof or to the area where control of undesirable vegetation is desired. Methods of application include, but are not limited to, pre-emergently contacting soil or water, post-emergently contacting the undesirable vegetation, or contacting the area adjacent to the undesirable vegetation.

As used herein, the term “vegetation” can include, for instance, dormant seeds, germinating seeds, emerging seedlings, plants propagating from vegetative propagules, immature vegetation, and established vegetation.

As used herein, the term “crop” refers to desired vegetation, for instance, plants that are grown to provide food, shelter, pasture, erosion control, etc. Example crops include cereals, legumes, vegetables, turf, grasslands, orchard and timber trees, grapevines, etc. Preferably, herbicides or herbicidal compositions have zero or minimal herbicidal effect on crops.

As used herein, the term “undesirable vegetation” refers to vegetation that is not wanted in a given area, for instance, weed species. Herbicides or herbicidal compositions are used to control undesirable vegetation. Preferably, herbicides or herbicidal compositions have a large or complete herbicidal effect on undesirable vegetation.

As used herein, “active ingredient” or “ai” may be understood to include a chemical compound or composition that has an effect on vegetation; specifically, a herbicidal effect or a safening effect on the vegetation.

As used herein, “acid equivalent” or “ae” may be understood to include the amount of the acid form of an active ingredient that is calculated from the amount of a salt or ester form of that active ingredient. For example, if the acid form of an active ingredient “Z” has a molecular weight of 100 Dalton, and the salt form of Z has a molecular weight of 130 Dalton, an application of 130 g ai/ha of the Z salt would be equal to applying 100 g ae/ha of the acid form of Z:

130 g ai/ha Z salt*(100 Da Z acid/130 Da Z salt)=100 g ae/ha Z acid.

As used herein, unless otherwise specified, the term “acyl” may be understood to include a group of formula —C(O)R, where “C(O)” is short-hand notation for C═O. In the acyl group, the R may be alkyl (e.g., C₁-C₆ alkyl), haloalkyl (e.g., C₁-C₆ haloalkyl), alkenyl (e.g., C₂-C₆ alkenyl), haloalkenyl (e.g., C₂-C₆ haloalkenyl), alkynyl (e.g., C₂-C₆ alkynyl), aryl or heteroaryl, or arylalkyl (e.g., C₇-C₁₀ arylalkyl.

As used herein, the term “alkyl” may be understood to include saturated, straight-chained, branched, or cyclic saturated hydrocarbon moieties. Unless otherwise specified, C₁-C₂₀ (e.g., C₁-C₁₂, C₁-C₁₀, C₁-C₈, C₁-C₆, or C₁-C₄) alkyl groups are intended. Examples of alkyl groups include methyl, ethyl, propyl, cyclopropyl, 1-methyl-ethyl, butyl, cyclobutyl, 1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl-ethyl, pentyl, cyclopentyl, 1-methyl-butyl, 2-methyl-butyl, 3-methyl-butyl, 2,2-dimethyl-propyl, 1-ethyl-propyl, hexyl, cyclohexyl, 1,1-dimethyl-propyl, 1,2-dimethyl-propyl, 1-methyl-pentyl, 2-methyl-pentyl, 3-methyl-pentyl, 4-methyl-pentyl, 1,1-dimethyl-butyl, 1,2-dimethyl-butyl, 1,3-dimethyl-butyl, 2,2-dimethyl-butyl, 2,3-dimethyl-butyl, 3,3-dimethyl-butyl, 1-ethyl-butyl, 2-ethyl-butyl, 1,1,2-trimethyl-propyl, 1,2,2-trimethyl-propyl, 1-ethyl-1-methyl-propyl, and 1-ethyl-2-methyl-propyl. Alkyl substituents may also be substituted with one or more chemical moieties. Examples of suitable substituents include, for example, hydroxy, nitro, cyano, formyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ acyl, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ haloalkylsulfinyl, C₁-C₆ alkylsulfonyl, C₁-C₆ haloalkylsulfonyl, C₁-C₆ alkoxycarbonyl, C₁-C₆ haloalkoxycarbonyl, C₁-C₆ carbamoyl, C₁-C₆ halocarbamoyl, hydroxycarbonyl, C₁-C₆ alkylcarbonyl, C₁-C₆ haloalkylcarbonyl, aminocarbonyl, C₁-C₆ alkylaminocarbonyl, haloalkylaminocarbonyl, C₁-C₆ dialkylaminocarbonyl, and C₁-C₆ dihaloalkylaminocarbonyl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied. Preferred substituents include cyano and C₁-C₆ alkoxy.

As used herein, the term “haloalkyl” may be understood to include alkyl groups wherein the hydrogen atoms may partially or entirely be substituted with halogen atoms. Unless otherwise specified, C₁-C₂₀ (e.g., C₁-C₁₂, C₁-C₁₀, C₁-C₈, C₁-C₆, or C₁-C₄) alkyl groups are intended. Examples include chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, and 1,1,1-trifluoroprop-2-yl. Haloalkyl substituents may also be substituted with one or more chemical moieties. Examples of suitable substituents include, for example, hydroxy, nitro, cyano, formyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ acyl, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ haloalkylsulfinyl, C₁-C₆ alkylsulfonyl, C₁-C₆ haloalkylsulfonyl, C₁-C₆ alkoxycarbonyl, C₁-C₆ haloalkoxycarbonyl, C₁-C₆ carbamoyl, C₁-C₆ halocarbamoyl, hydroxycarbonyl, C₁-C₆ alkylcarbonyl, C₁-C₆ haloalkylcarbonyl, aminocarbonyl, C₁-C₆ alkylaminocarbonyl, haloalkylaminocarbonyl, C₁-C₆ dialkylaminocarbonyl, and C₁-C₆ dihaloalkylaminocarbonyl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied. Preferred substituents include cyano and C₁-C₆ alkoxy.

As used herein, the term “alkoxy” may be understood to include a group of the formula R—O—, where R is unsubstituted or substituted alkyl as defined above. Unless otherwise specified, alkoxy groups wherein R is a C₁-C₂₀ (e.g., C₁-C₁₂, C₁-C₁₀, C₁-C₈, C₁-C₆, or C₁-C₄) alkyl group are intended. Examples include methoxy, ethoxy, propoxy, 1-methyl-ethoxy, butoxy, 1-methyl-propoxy, 2-methyl-propoxy, 1,1-dimethyl-ethoxy, pentoxy, 1-methyl-butyloxy, 2-methyl-butoxy, 3-methyl-butoxy, 2,2-dimethyl-propoxy, 1-ethyl-propoxy, hexoxy, 1,1-dimethyl-propoxy, 1,2-dimethyl-propoxy, 1-methyl-pentoxy, 2-methyl-pentoxy, 3-methyl-pentoxy, 4-methyl-penoxy, 1,1-dimethyl-butoxy, 1,2-dimethyl-butoxy, 1,3-dimethyl-butoxy, 2,2-dimethyl-butoxy, 2,3-dimethyl-butoxy, 3,3-dimethyl-butoxy, 1-ethyl-butoxy, 2-ethylbutoxy, 1,1,2-trimethyl-propoxy, 1,2,2-trimethyl-propoxy, 1-ethyl-1-methyl-propoxy, and 1-ethyl-2-methyl-propoxy.

As used herein, the term “alkoxycarbonyl” may be understood to include a group of the formula —C(O)OR, where R is an unsubstituted or substituted alkyl as defined above. Unless otherwise specified, alkoxycarbonyl groups wherein R is a C₁-C₂₀ (e.g., C₁-C₁₂, C₁-C₁₀, C₁-C₈, C₁-C₆, or C₁-C₄) alkyl group are intended. Examples include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 1-methyl-ethoxycarbonyl, butoxycarbonyl, 1-methyl-propoxycarbonyl, 2-methyl-propoxycarbonyl, 1,1-dimethyl-ethoxycarbonyl, pentoxycarbonyl, 1-methyl-butyloxycarbonyl, 2-methyl-butoxycarbonyl, 3-methyl-butoxycarbonyl, 2,2-dimethyl-propoxycarbonyl, 1-ethyl-propoxycarbonyl, hexoxycarbonyl, 1,1-dimethyl-propoxycarbonyl, 1,2-dimethyl-propoxycarbonyl, 1-methyl-pentoxycarbonyl, 2-methyl-pentoxycarbonyl, 3-methyl-pentoxycarbonyl, 4-methyl-penoxycarbonyl, 1,1-dimethyl-butoxycarbonyl, 1,2-dimethyl-butoxycarbonyl, 1,3-dimethyl-butoxycarbonyl, 2,2-dimethyl-butoxycarbonyl, 2,3-dimethyl-butoxycarbonyl, 3,3-dimethyl-butoxycarbonyl, 1-ethyl-butoxycarbonyl, 2-ethylbutoxycarbonyl, 1,1,2-trimethyl-propoxycarbonyl, 1,2,2-trimethyl-propoxycarbonyl, 1-ethyl-1-methyl-propoxycarbonyl, and 1-ethyl-2-methyl-propoxycarbonyl.

As used herein, the term “haloalkoxy” may be understood to include a group of the formula R—O—, where R is unsubstituted or substituted haloalkyl as defined above. Unless otherwise specified, haloalkoxy groups wherein R is a C₁-C₂₀ (e.g., C₁-C₁₂, C₁-C₁₀, C₁-C₈, C₁-C₆, or C₁-C₄) alkyl group are intended. Examples include chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, and 1,1,1-trifluoroprop-2-oxy.

As used herein, the term “aryl,” as well as derivative terms such as aryloxy, may be understood to include groups that include a monovalent aromatic carbocyclic group of from 6 to 14 carbon atoms. Aryl groups can include a single ring or multiple condensed rings. In some aspects, aryl groups include C₆-C₁₀ aryl groups. Examples of aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, tetrahydronaphthyl, phenylcyclopropyl, and indanyl. In some aspects, the aryl group can be a phenyl, indanyl or naphthyl group.

As used herein, the term “heteroaryl,” as well as derivative terms such as “heteroaryloxy,” may be understood to include a 5- or 6-membered aromatic ring containing one or more heteroatoms, for example, N, O or S. Heteroaryl rings may be fused to other aromatic systems. The aryl or heteroaryl substituents may also be substituted with one or more chemical moieties. Examples of suitable substituents include, for example, hydroxy, nitro, cyano, formyl, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₆ alkoxy, C₁-C₆ haloalkyl, C₁-C₆ haloalkoxy, C₁-C₆ acyl, C₁-C₆ alkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ alkylsulfonyl, C₁-C₆ alkoxycarbonyl, C₁-C₆ carbamoyl, hydroxycarbonyl, C₁-C₆ alkylcarbonyl, aminocarbonyl, C₁-C₆alkylaminocarbonyl, C₁-C₆ dialkylaminocarbonyl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied. Preferred substituents include halogen, C₁-C₄ alkyl and C₁-C₄ haloalkyl.

As used herein, the term “halogen,” including derivative terms such as “halo,” refers to fluorine, chlorine, bromine and iodine.

As used herein, agriculturally acceptable salts and esters may be understood to include salts and esters that exhibit herbicidal activity, or that are or can be converted in plants, water, or soil to the referenced herbicide. Exemplary agriculturally acceptable esters are those that are or can be hydrolyzed, oxidized, metabolized, or otherwise converted, e.g., in plants, water, or soil, to the corresponding carboxylic acid which, depending on the pH, may be in the dissociated or undissociated form.

Compounds described herein can include N-oxides. Pyridine N-oxides can be obtained by oxidation of the corresponding pyridines. Suitable oxidation methods are described, for example, in Houben-Weyl, Methoden der organischen Chemie [Methods in organic chemistry], expanded and subsequent volumes to the 4th edition, volume E 7b, p. 565 f.

II. Pyridine Carboxylate Herbicides

Compositions and methods of the present disclosure include a safened composition comprising (a) a pyridine carboxylate herbicide defined by Formula (I):

wherein:

-   -   R¹ is cyanomethyl or propargyl;     -   R² and R^(2′) are independently hydrogen, C₁-C₆ alkyl, formyl,         alkoxycarbonyl, or acyl;     -   R³, R^(3′), R^(3″), and R^(3″) are independently hydrogen,         halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₃alkoxy, or C₁-C₃         haloalkoxy;         or an agriculturally acceptable N-oxide, salt, or ester thereof;         and         (b) a safener comprising cloquintocet or an agriculturally         acceptable salt or ester thereof.

In some aspects, compositions and methods of the present disclosure include the safened composition comprising (a) the pyridine carboxylate herbicide cyanomethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, Compound A:

or an agriculturally acceptable N-oxide, salt, or ester thereof, and (b) a safener comprising cloquintocet or an agriculturally acceptable salt or ester thereof.

In some aspects, compositions and methods of the present disclosure include the safened composition comprising (a) the pyridine carboxylate herbicide propargyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, Compound B:

or an agriculturally acceptable N-oxide, salt, or ester thereof, and (b) a safener comprising cloquintocet or an agriculturally acceptable salt or ester thereof.

Pyridine carboxylate herbicides defined by Formula (I), as well as methods of making these pyridine carboxylate herbicides, are disclosed in application PCT/US2018/031004, filed May 4, 2018, the entire disclosure of which is hereby expressly incorporated by reference.

In some aspects, the pyridine carboxylate herbicide can be provided as an agriculturally acceptable salt. Exemplary agriculturally acceptable salts of the pyridine carboxylate herbicides include, but are not limited to: sodium salts; potassium salts; ammonium salts or substituted ammonium salts, in particular mono-, di- and tri-C₁-C₈-alkylammonium salts such as methyl ammonium, dimethylammonium and isopropylammonium; mono-, di- and tri-hydroxy-C₂-C₈-alkylammonium salts such as hydroxyethylammonium, di(hydroxyethyl)ammonium, tri(hydroxyethyl)ammonium, hydroxypropylammonium, di(hydroxypropyl)ammonium and tri(hydroxypropyl)ammonium salts; olamine salts; diglycolamine salts; choline salts; and quaternary ammonium salts such as those represented by the formula R⁹R¹⁰R¹¹R¹²N+ and wherein R⁹, R¹⁰, R¹¹ and R¹² (e.g., R⁹-R¹²) each independently can represent hydrogen, C₁-C₁₀ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₁-C₈ alkoxy, C₁-C₈ alkylthio, or aryl groups, provided that R⁹-R¹² are sterically compatible.

In some aspects, the pyridine carboxylate herbicide can be provided as an agriculturally acceptable ester. Exemplary agriculturally acceptable esters of the pyridine carboxylate herbicides include, but are not limited to: methyl, ethyl, propyl, 1-methyl-ethyl, butyl, 1-methyl-propyl, 2-methyl-propyl, pentyl, 1-methyl-butyl, 2-methyl-butyl, 3-methyl-butyl, 1-ethyl-propyl, hexyl, 1-methyl-hexyl (mexyl), 2-ethylhexyl, heptyl, 1-methyl-heptyl (meptyl), octyl, isooctyl (isoctyl), butoxyethyl (butotyl), and benzyl.

The pyridine carboxylate herbicide, or an agriculturally acceptable N-oxide, salt, or ester thereof, can be applied to vegetation or an area adjacent the vegetation or applied to soil or water to prevent the emergence or growth of vegetation in an amount sufficient to induce a herbicidal effect. In some aspects, the pyridine carboxylate herbicide, or an agriculturally acceptable N-oxide, salt, or ester thereof, is applied to vegetation or an area adjacent the vegetation or applied to soil or water to prevent the emergence or growth of vegetation in an amount of 0.1 grams acid equivalent per hectare (g ae/ha) or greater, such as 0.2 g ae/ha or greater, 0.3 g ae/ha or greater, 0.4 g ae/ha or greater, 0.5 g ae/ha or greater, 0.6 g ae/ha or greater, 0.7 g ae/ha or greater, 0.8 g ae/ha or greater, 0.9 g ae/ha or greater, 1 g ae/ha or greater, 1.1 g ae/ha or greater, 1.2 g ae/ha or greater, 1.3 g ae/ha or greater, 1.4 g ae/ha or greater, 1.5 g ae/ha or greater, 1.6 g ae/ha or greater, 1.7 g ae/ha or greater, 1.8 g ae/ha or greater, 1.9 g ae/ha or greater, 2 g ae/ha or greater, 2.25 g ae/ha or greater, 2.5 g ae/ha or greater, 2.75 g ae/ha or greater, 3 g ae/ha or greater, 4 g ae/ha or greater, 5 g ae/ha or greater, 6 g ae/ha or greater, 7 g ae/ha or greater, 8 g ae/ha or greater, 9 g ae/ha or greater, 10 g ae/ha or greater, 11 g ae/ha or greater, 12 g ae/ha or greater, 13 g ae/ha or greater, 14 g ae/ha or greater, 15 g ae/ha or greater, 16 g ae/ha or greater, 17 g ae/ha or greater, 18 g ae/ha or greater, 19 g ae/ha or greater, 20 g ae/ha or greater, 22 g ae/ha or greater, 24 g ae/ha or greater, 25 g ae/ha or greater, 26 g ae/ha or greater, 28 g ae/ha or greater, 30 g ae/ha or greater, 32 g ae/ha or greater, 34 g ae/ha or greater, 35 g ae/ha or greater, 36 g ae/ha or greater, 38 g ae/ha or greater, 40 g ae/ha or greater, 42.5 g ae/ha or greater, 45 g ae/ha or greater, 47.5 g ae/ha or greater, 50 g ae/ha or greater, 52.5 g ae/ha or greater, 55 g ae/ha or greater, 57.5 g ae/ha or greater, 60 g ae/ha or greater, 65 g ae/ha or greater, 70 g ae/ha or greater, 75 g ae/ha or greater, 80 g ae/ha or greater, 85 g ae/ha or greater, 90 g ae/ha or greater, 95 g ae/ha or greater, 100 g ae/ha or greater, 110 g ae/ha or greater, 120 g ae/ha or greater, 130 g ae/ha or greater, 140 g ae/ha or greater, 150 g ae/ha or greater, 160 g ae/ha or greater, 170 g ae/ha or greater, 180 g ae/ha or greater, 190 g ae/ha or greater, 200 g ae/ha or greater, 210 g ae/ha or greater, 220 g ae/ha or greater, 230 g ae/ha or greater, 240 g ae/ha or greater, 250 g ae/ha or greater, 260 g ae/ha or greater, 270 g ae/ha or greater, 280 g ae/ha or greater, or 290 g ae/ha or greater; in an amount of 300 g ae/ha or less, such as 290 g ae/ha or less, 280 g ae/ha or less, 270 g ae/ha or less, 260 g ae/ha or less, 250 g ae/ha or less, 240 g ae/ha or less, 230 g ae/ha or less, 220 g ae/ha or less, 210 g ae/ha or less, 200 g ae/ha or less, 190 g ae/ha or less, 180 g ae/ha or less, 170 g ae/ha or less, 160 g ae/ha or less, 150 g ae/ha or less, 140 g ae/ha or less, 130 g ae/ha or less, 120 g ae/ha or less, 110 g ae/ha or less, 100 g ae/ha or less, 95 g ae/ha or less, 90 g ae/ha or less, 85 g ae/ha or less, 80 g ae/ha or less, 75 g ae/ha or less, 70 g ae/ha or less, 65 g ae/ha or less, 60 g ae/ha or less, 57.5 g ae/ha or less, 55 g ae/ha or less, 52.5 g ae/ha or less, 50 g ae/ha or less, 47.5 g ae/ha or less, 45 g ae/ha or less, 42.5 g ae/ha or less, 40 g ae/ha or less, 38 g ae/ha or less, 36 g ae/ha or less, 35 g ae/ha or less, 34 g ae/ha or less, 32 g ae/ha or less, 30 g ae/ha or less, 28 g ae/ha or less, 26 g ae/ha or less, 25 g ae/ha or less, 24 g ae/ha or less, 22 g ae/ha or less, 20 g ae/ha or less, 19 g ae/ha or less, 18 g ae/ha or less, 17 g ae/ha or less, 16 g ae/ha or less, 15 g ae/ha or less, 14 g ae/ha or less, 13 g ae/ha or less, 12 g ae/ha or less, 11 g ae/ha or less, 10 g ae/ha or less, 9 g ae/ha or less, 8 g ae/ha or less, 7 g ae/ha or less, 6 g ae/ha or less, 5 g ae/ha or less, 4 g ae/ha or less, 3 g ae/ha or less, 2.75 g ae/ha or less, 2.5 g ae/ha or less, 2.25 g ae/ha or less, 2 g ae/ha or less, 1.9 g ae/ha or less, 1.8 g ae/ha or less, 1.7 g ae/ha or less, 1.6 g ae/ha or less, 1.5 g ae/ha or less, 1.4 g ae/ha or less, 1.3 g ae/ha or less, 1.2 g ae/ha or less, 1.1 g ae/ha or less, 1 g ae/ha or less, 0.9 g ae/ha or less, 0.8 g ae/ha or less, 0.7 g ae/ha or less, 0.6 g ae/ha or less, 0.5 g ae/ha or less, 0.4 g ae/ha or less, 0.3 g ae/ha or less, or 0.2 g ae/ha or less; or in an amount within any range defined between any pair of the preceding values, such as from 0.1 g ae/ha to 300 g ae/ha, from 1 g ae/ha to 150 g ae/ha, from 10 g ae/ha to 200 g ae/ha, from 25 g ae/ha to 75 g ae/ha, or from 40 g ae/ha to 100 g ae/ha.

III. Cloquintocet

In addition to the pyridine carboxylate herbicide, the compositions and methods of the present disclosure can include a quinolinoxyacetate safener or an agriculturally acceptable salt or ester thereof. Herbicide safeners are molecules used in combination with herbicides to make them “safer”—that is, to reduce the herbicidal effect of the herbicide on crop plants and to improve selectivity between crops and the undesirable vegetation being targeted by the herbicide. Herbicide safeners can be used to pre-treat crop seeds prior to planting. Safeners may also be sprayed on plants as a mixture with the herbicide, or separately and sequentially with the herbicide.

Quinolinoxyacetate safeners are known in the art and described, for example, in U.S. Pat. No. 4,902,340 and U.S. Patent Application Publication No. 2014/0031224, the disclosures of which are both incorporated by reference herein. Quinolinoxyacetate safeners include, for example, cloquintocet and the derivatives thereof. Cloquintocet is a quinoline compound having the following chemical structure:

This form of cloquintocet may also be referred to as “cloquintocet-acid.”

In some aspects, the safener can comprise an agriculturally acceptable salt of cloquintocet. Agriculturally acceptable salts of cloquintocet include, for example sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, monoisopropanolammonium, diisopropanolammonium, triisopropanolammonium, choline, N,N-dimethylethanolammonium, diethylammonium, dimethylammonium, trimethylammonium, triethylammonium, and isopropylammonium salts of cloquintocet.

In some aspects, the safener can comprise an agriculturally acceptable ester of cloquintocet. Agriculturally acceptable esters of cloquintocet include, for example, the methyl, ethyl, propyl, butyl, or methylhexyl (also known as mexyl) ester of cloquintocet. In some aspects, the safener comprises cloquintocet-mexyl, the structure of which is shown below.

In some aspects, the safener can comprise cloquintocet-acid, an agriculturally acceptable salt of cloquintocet, an agriculturally acceptable ester of cloquintocet, or mixtures thereof. Cloquintocet can be a safener when applied in combination with herbicides and can be used to reduce phytotoxicity to crops such as wheat, barley, triticale, rye, teff, oats, maize, sorghum, rice, millet, canola/oilseed rape, sunflower, sugar beet, cotton, sugarcane, and pasture grasses. In some aspects, the undesirable vegetation is in broadleaf crops. In some aspects, the undesirable vegetation is in canola, flax, sunflower, soy, or cotton.

Cloquintocet or an agriculturally acceptable salt or ester thereof can be used in an amount sufficient to induce a safening effect. In some aspects, cloquintocet or an agriculturally acceptable salt or ester thereof is applied to vegetation or an area adjacent the vegetation or applied to soil or water in an amount of 1 g active ingredient per hectare (ai/ha) or greater, such as 2 g ai/ha or greater, 3 g ai/ha or greater, 4 g ai/ha or greater, 5 g ai/ha or greater, 6 g ai/ha or greater, 7 g ai/ha or greater, 8 g ai/ha or greater, 9 g ai/ha or greater, 10 g ai/ha or greater, 11 g ai/ha or greater, 12 g ai/ha or greater, 13 g ai/ha or greater, 14 g ai/ha or greater, 15 g ai/ha or greater, 16 g ai/ha or greater, 17 g ai/ha or greater, 18 g ai/ha or greater, 19 g ai/ha or greater, 20 g ai/ha or greater, 22 g ai/ha or greater, 24 g ai/ha or greater, 25 g ai/ha or greater, 26 g ai/ha or greater, 28 g ai/ha or greater, 30 g ai/ha or greater, 32 g ai/ha or greater, 34 g ai/ha or greater, 35 g ai/ha or greater, 36 g ai/ha or greater, 38 g ai/ha or greater, 40 g ai/ha or greater, 42.5 g ai/ha or greater, 45 g ai/ha or greater, 47.5 g ai/ha or greater, 50 g ai/ha or greater, 52.5 g ai/ha or greater, 55 g ai/ha or greater, 57.5 g ai/ha or greater, 60 g ai/ha or greater, 65 g ai/ha or greater, 70 g ai/ha or greater, 75 g ai/ha or greater, 80 g ai/ha or greater, 85 g ai/ha or greater, 90 g ai/ha or greater, 95 g ai/ha or greater, 100 g ai/ha or greater, 110 g ai/ha or greater, 120 g ai/ha or greater, 130 g ai/ha or greater, 140 g ai/ha or greater, 150 g ai/ha or greater, 160 g ai/ha or greater, 170 g ai/ha or greater, 180 g ai/ha or greater, 190 g ai/ha or greater, 200 g ai/ha or greater, 210 g ai/ha or greater, 220 g ai/ha or greater, 230 g ai/ha or greater, 240 g ai/ha or greater, 250 g ai/ha or greater, 260 g ai/ha or greater, 270 g ai/ha or greater, 280 g ai/ha or greater, or 290 g ai/ha or greater; in an amount of 300 g ai/ha or less such as 290 g ai/ha or less, 280 g ai/ha or less, 270 g ai/ha or less, 260 g a/ha or less, 250 g ai/ha or less, 240 g ai/ha or less, 230 g ai/ha or less, 220 g ai/ha or less, 210 g ai/ha or less, 200 g ai/ha or less, 190 g ai/ha or less, 180 g ai/ha or less, 170 g ai/ha or less, 160 g ai/ha or less, 150 g ai/ha or less, 140 g ai/ha or less, 130 g ai/ha or less, 120 g ai/ha or less, 110 g ai/ha or less, 100 g ai/ha or less, 95 g ai/ha or less, 90 g ai/ha or less, 85 g ai/ha or less, 80 g ai/ha or less, 75 g ai/ha or less, 70 g ai/ha or less, 65 g ai/ha or less, 60 g ai/ha or less, 57.5 g ai/ha or less, 55 g ai/ha or less, 52.5 g ai/ha or less, 50 g ai/ha or less, 47.5 g ai/ha or less, 45 g ai/ha or less, 42.5 g ai/ha or less, 40 g ai/ha or less, 38 g ai/ha or less, 36 g ai/ha or less, 35 g ai/ha or less, 34 g ai/ha or less, 32 g ai/ha or less, 30 g ai/ha or less, 28 g ai/ha or less, 26 g ai/ha or less, 25 g ai/ha or less, 24 g ai/ha or less, 22 g ai/ha or less, 20 g ai/ha or less, 19 g ai/ha or less, 18 g ai/ha or less, 17 g ai/ha or less, 16 g ai/ha or less, 15 g ai/ha or less, 14 g ai/ha or less, 13 g ai/ha or less, 12 g ai/ha or less, 11 g ai/ha or less, 10 g ai/ha or less, 9 g ai/ha or less, 8 g ai/ha or less, 7 g ai/ha or less, 6 g ai/ha or less, 5 g ai/ha or less, 4 g ai/ha or less, 3 g ai/ha or less, or 2 g ai/ha or less; or in an amount within any range defined between any pair of the preceding values, such as from 1 g ai/ha to 300 g ai/ha, from 5 g ai/ha to 150 g ai/ha, from 10 g ai/ha to 200 g ai/ha, from 20 g ai/ha to 75 g ai/ha, or from 40 g ai/ha to 100 g ai/ha.

IV. Safened Compositions

A safened composition comprising (a) a pyridine carboxylate herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof may be mixed with or applied in combination with (b) a safener comprising cloquintocet or an agriculturally acceptable salt or ester thereof.

In some aspects, (a) and (b) are used in an amount sufficient to induce an unexpectedly enhanced herbicidal effect (e.g., increased damage or injury to undesirable vegetation) while still showing good crop compatibility (e.g., no increased damage to crops or minimal increased damage or injury to crops) when compared to the individual application of the herbicidal compounds (a) or (b). In some aspects, the damage or injury to undesirable vegetation caused by the safened compositions and methods disclosed herein is evaluated using a scale from 0% to 100%, when compared with the untreated control vegetation, wherein 0% indicates no damage to the undesirable vegetation and 100% indicates complete destruction of the undesirable vegetation. Similarly, in some aspects, the damage or injury to the crop caused by the safened compositions and methods disclosed herein is evaluated using a scale from 0% to 100%, when compared with control crops treated with only the herbicide or the safener, wherein 0% indicates no damage to the crop and 100% indicates complete destruction of the crop.

In some aspects, the joint action of (a) the pyridine carboxylate herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof and (b) the cloquintocet safener or an agriculturally acceptable salt or ester thereof results in unexpectedly enhanced herbicidal effect against undesirable vegetation, even at application rates below those typically used for the herbicide to have a herbicidal effect on its own. In some aspects, the compositions and methods disclosed herein can, based on the individual components, be used at lower application rates to achieve a herbicidal effect comparable to the effect produced by the individual components at normal application rates. In some aspects, the joint action of (a) the pyridine carboxylate herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof and (b) the cloquintocet safener or an agriculturally acceptable salt or ester thereof results in an unexpected protective effect for desired crops against damage to the crops that might be caused by the herbicide alone.

In some aspects, the weight ratio of (a) the pyridine carboxylate herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof (in g ae/ha) to (b) the cloquintocet safener or an agriculturally acceptable salt or ester thereof (in g ai/ha) can be 1:5 or more, such as 1:4.75 or more, 1:4.5 or more, 1:4.25 or more, 1:4 or more, 1:3.75 or more, 1:3.5 or more, 1:3.25 or more, 1:3 or more, 1:2.75 or more, 1:2.5 or more, 1:2.25 or more, 1:2 or more, 1:1.9 or more, 1:1.8 or more, 1:1.7 or more, 1:1.6 or more, 1:1.5 or more, 1:1.4 or more, 1:1.3 or more, 1:1.2 or more, 1:1.1 or more, 1:1 or more, 1.1:1 or more, 1.2:1 or more, 1.3:1 or more, 1.4:1 or more, 1.5:1 or more, 1.6:1 or more, 1.7:1 or more, 1.8:1 or more, 1.9:1 or more, 2:1 or more, 2.25:1 or more, 2.5:1 or more, 2.75:1 or more, 3:1 or more, 3.25:1 or more, 3.5:1 or more, 3.75:1 or more, 4:1 or more, 4.25:1 or more, 4.5:1 or more, 4.75:1 or more, 5:1 or more, 6:1 or more, 7:1 or more, 8:1 or more, 9:1 or more, 10:1 or more, 11:1 or more, 12:1 or more, 13:1 or more, 14:1 or more, 15:1 or more, 16:1 or more, 17:1 or more, 18:1 or more, 19:1 or more, 20:1 or more, 25:1 or more, 30:1 or more, 35:1 or more, 40:1 or more, 45:1 or more, 50:1 or more, 55:1 or more, or 60:1 or more; the weight ratio of (a) to (b) can be 65:1 or less, such as 60:1 or less, 55:1 or less, 50:1 or less, 45:1 or less, 40:1 or less, 35:1 or less, 30:1 or less, 25:1 or less, 20:1 or less, 19:1 or less, 18:1 or less, 17:1 or less, 16:1 or less, 15:1 or less, 14:1 or less, 13:1 or less, 12:1 or less, 11:1 or less, 10:1 or less, 9:1 or less, 8:1 or less, 7:1 or less, 6:1 or less, 5:1 or less, 4.75:1 or less, 4.5:1 or less, 4.25:1 or less, 4:1 or less, 3.75:1 or less, 3.5:1 or less, 3.25:1 or less, 3:1 or less, 2.75:1 or less, 2.5:1 or less, 2.25:1 or less, 2:1 or less, 1.9:1 or less, 1.8:1 or less, 1.7:1 or less, 1.6:1 or less, 1.5:1 or less, 1.4:1 or less, 1.3:1 or less, 1.2:1 or less, 1.1:1 or less, 1:1 or less, 1:1.1 or less, 1:1.2 or less, 1:1.3 or less, 1:1.4 or less, 1:1.5 or less, 1:1.6 or less, 1:1.7 or less, 1:1.8 or less, 1:1.9 or less, 1:2 or less, 1:2.25 or less, 1:2.5 or less, 1:2.75 or less, 1:3 or less, 1:3.25 or less, 1:3.5 or less, 1:3.75 or less, 1:4 or less, 1:4.25 or less, 1:4.5 or less, or 1:4.75 or less; or the weight ratio of (a) to (b) can range from any of the minimum ratios to any of the maximum ratios provided above, such as from 1:5 to 65:1, from 1:2 to 25:1, from 1:1 to 15:1, from 1:3 to 4:1, or from 1:1.5 to 10:1.

In some aspects, (a) and (b), independently, can be employed in a purity of from 90% to 100% (e.g., from 95% to 100%) according to nuclear magnetic resonance (NMR) spectroscopy.

V. Formulations

The present disclosure also includes formulations of the compositions and methods disclosed herein.

A. Additives

The compositions and methods disclosed herein can also be mixed with or applied with an additive. In some aspects, the additive is added sequentially. In some aspects, the additive is added simultaneously. In some aspects, the additive is premixed with the pyridine carboxylate herbicide or agriculturally acceptable N-oxide, salt, or ester thereof. In some aspects, the additive is premixed with the cloquintocet safener or agriculturally acceptable salt or ester thereof.

1. Other Pesticides

Some aspects of the safened compositions includes adding one or more additional pesticide active ingredients to the safened compositions. These pesticide active ingredients may include one or more of an herbicide, an insecticide, a fungicide, a nematocide, a miticide, a arthropodicide, a bactericide, a plant growth regulator, or combinations thereof that are compatible with the compositions of the present disclosure.

In some aspects, the additive is an additional herbicide. For example, the compositions described herein can be applied in conjunction with one or more additional herbicides to control undesirable vegetation. The composition can be formulated with the one or more additional herbicides, tank mixed with the one or more additional herbicides, or applied sequentially with the one or more additional herbicides. Exemplary additional herbicides include, but are not limited to. 4-CPA; 4-CPB; 4-CPP; 2;4-D; 2;4-D choline salt; 2,4-D salts, esters and amines; 2,4-DB; 3,4-DA; 3,4-DB; 2,4-DEB; 2,4-DEP; 2,4-DP; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor; acifluorfen; aclonifen; acrolein; alachlor; allidochlor; alloxydim; allyl alcohol; alorac; ametridione; ametryne; amibuzin; amicarbazone; amidosulfuron; aminocyclopyrachlor; 4-aminopicolinic acid based herbicides, such as halauxifen, halauxifen-methyl, florpyrauxifen, and those described in U.S. Pat. Nos. 7,314,849 and 7,432,227 to Balko, et al.; aminopyralid; amiprofos-methyl; amitrole; ammonium sulfamate; anilofos; anisuron; asulam; atraton; atrazine; azafenidin; azimsulfuron; aziprotryne; barban; BCPC; beflubutamid; benazolin; bencarbazone; benfluralin; benfuresate; bensulide; bensulfuron; benthiocarb; bentazone; benzadox; benzfendizone; benzipram; benzobicyclon; benzofenap; benzofluor; benzoylprop; benzthiazuron; bialaphos; bicyclopyrone; bifenox; bilanafos; bispyribac; borax; bromacil; bromobonil; bromobutide; bromofenoxim; bromoxynil; brompyrazon; butachlor; butafenacil; butamifos; butenachlor; buthidazole; buthiuron; butralin; butroxydim; buturon; butylate; cacodylic acid; cafenstrole; calcium chlorate; calcium cyanamide; cambendichlor; carbasulam; carbetamide; carboxazole; chlorprocarb; carfentrazone-ethyl; CDEA; CEPC; chlomethoxyfen; chloramben; chloranocryl; chlorazifop; chlorazine; chlorobromuron; chlorbufam; chloreturon; chlorfenac; chlorfenprop; chlorflurazole; chlorflurenol; chloridazon; chlorimuron; chlornitrofen; chloropon; chlorotoluron; chloroxuron; chloroxynil; chlorpropham; chlorsulfuron; chlorthal; chlorthiamid; cinidon-ethyl; cinmethylin; cinosulfuron; cisanilide; clacyfos; clethodim; cliodinate; clodinafop-propargyl; clofop; clomazone; clomeprop; cloprop; cloproxydim; clopyralid; cloransulam-methyl; CMA; copper sulfate; CPMF; CPPC; credazine; cresol; cumyluron; cyanatryn; cyanazine; cycloate; cyclopyrimorate; cyclosulfamuron; cycloxydim; cycluron; cyhalofop-butyl; cyperquat; cyprazine; cyprazole; cypromid; daimuron; dalapon; dazomet; delachlor; desmedipham; desmetryn; di-allate; dicamba; dichlobenil; dichloralurea; dichlormate; dichlorprop; dichlorprop-P; diclofop-methyl; diclosulam; diethamquat; diethatyl; difenopenten; difenoxuron; difenzoquat; diflufenican; diflufenzopyr; dimefuron; dimepiperate; dimethachlor; dimethametryn; dimethenamid; dimethenamid-P; dimexano; dimidazon; dinitramine; dinofenate; dinoprop; dinosam; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; disul; dithiopyr; diuron; DMPA; DNOC; DSMA; EBEP; eglinazine; endothal; epronaz; EPTC; erbon; esprocarb; ethalfluralin; ethametsulfuron; ethbenzamide; ethametsulfuron; ethidimuron; ethiolate; ethobenzamid; ethofumesate; ethoxyfen; ethoxysulfuron; etinofen; etnipromid; etobenzanid; EXD; fenasulam; fenoprop; fenoxaprop; fenoxaprop-P-ethyl; fenoxaprop-P-ethyl+isoxadifen-ethyl; fenoxasulfone; fenquinotrione; fenteracol; fenthiaprop; fentrazamide; fenuron; ferrous sulfate; flamprop; flamprop-M; flazasulfuron; florasulam; fluazifop; fluazifop-P-butyl; fluazolate; flucarbazone; flucetosulfuron; fluchloralin; flufenacet; flufenican; flufenpyr-ethyl; flumetsulam; flumezin; flumiclorac-pentyl; flumioxazin; flumipropyn; fluometuron; fluorodifen; fluoroglycofen; fluoromidine; fluoronitrofen; fluothiuron; flupoxam; flupropacil; flupropanate; flupyrsulfuron; fluridone; flurochloridone; fluroxypyr; fluroxypyr-meptyl; flurtamone; fluthiacet; fomesafen; foramsulfuron; fosamine; fumiclorac; furyloxyfen; glufosinate; glufosinate-ammonium; glufosinate-P-ammonium; glyphosate salts and esters; halosafen; halosulfuron; haloxydine; haloxyfop; hexachloroacetone; hexaflurate; hexazinone; imazamethabenz; imazamox; imazapic; imazapyr; imazaquin; imazethapyr; imazosulfuron; indanofan; indaziflam; iodobonil; iodomethane; iodosulfuron; iodosulfuron-ethyl-sodium; iofensulfuron; ioxynil; ipazine; ipfencarbazone; iprymidam; isocarbamid; isocil; isomethiozin; isonoruron; isopolinate; isopropalin; isoproturon; isouron; isoxaben; isoxachlortole; isoxaflutole; isoxapyrifop; karbutilate; ketospiradox; lactofen; lenacil; linuron; MAA; MAMA; MCPA esters and amines; MCPA-thioethyl; MCPB; mecoprop; mecoprop-P; medinoterb; mefenacet; mefluidide; mesoprazine; mesosulfuron; mesotrione; metam; metamifop; metamitron; metazachlor; metflurazon; methabenzthiazuron; methalpropalin; methazole; methiobencarb; methiozolin; methiuron; methometon; methoprotryne; methyl bromide; methyl isothiocyanate; methyldymron; metobenzuron; metobromuron; metolachlor; metosulam; metoxuron; metribuzin; metsulfuron; molinate; monalide; monisouron; monochloroacetic acid; monolinuron; monuron; morfamquat; MSMA; naproanilide; napropamide; napropamide-M; naptalam; neburon; nicosulfuron; nipyraclofen; nitralin; nitrofen; nitrofluorfen; norflurazon; noruron; OCH; orbencarb; ortho-dichlorobenzene; orthosulfamuron; oryzalin; oxadiargyl; oxadiazon; oxapyrazon; oxasulfuron; oxaziclomefone; oxyfluorfen; paraflufen-ethyl; parafluron; paraquat; pebulate; pelargonic acid; pendimethalin; penoxsulam; pentachlorophenol; pentanochlor; pentoxazone; perfluidone; pethoxamid; phenisopham; phenmedipham; phenmedipham-ethyl; phenobenzuron; phenylmercury acetate; picloram; picolinafen; pinoxaden; piperophos; potassium arsenite; potassium azide; potassium cyanate; pretilachlor; primisulfuron; procyazine; prodiamine; profluazol; profluralin; profoxydim; proglinazine; prohexadione-calcium; prometon; prometryne; pronamide; propachlor; propanil; propaquizafop; propazine; propham; propisochlor; propoxycarbazone; propyrisulfuron; propyzamide; prosulfalin; prosulfocarb; prosulfuron; proxan; prynachlor; pydanon; pyraclonil; pyraflufen; pyrasulfotole; pyrazogyl; pyrazone; pyrazolynate; pyrazosulfuron; pyrazoxyfen; pyribenzoxim; pyributicarb; pyriclor; pyridafol; pyridate; pyriftalid; pyriminobac; pyrimisulfan; pyrithiobac-sodium; pyroxasulfone; pyroxsulam; quinclorac; quinmerac; quinoclamine; quinonamid; quizalofop; quizalofop-P-ethyl; quizalofop-P-tefuryl; rhodethanil; rimsulfuron; saflufenacil; S-metolachlor; sebuthylazine; secbumeton; sethoxydim; siduron; simazine; simeton; simetryn; SMA; sodium arsenite; sodium azide; sodium chlorate; sulcotrione; sulfallate; sulfentrazone; sulfometuron; sulfosate; sulfosulfuron; sulfuric acid; sulglycapin; swep; TCA; tebutam; tebuthiuron; tefuryltrione; tembotrione; tepraloxydim; terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryne; tetrafluron; thenylchlor; thiameturon; thiazafluron; thiazopyr; thidiazimin; thidiazuron; thiencarbazone; thifensulfuron; thiobencarb; tiafenacil; tiocarbazil; tioclorim; tolpyralate; topramezone; tralkoxydim; tri-allate; triafamone; triasulfuron; triaziflam; tribenuron; tribenuron; tricamba; triclopyr choline salt; triclopyr esters and amines; tridiphane; trietazine; trifloxysulfuron; trifludimoxazin; trifluralin; triflusulfuron; trifop; trifopsime; trihydroxytriazine; trimeturon; tripropindan; tritac; tritosulfuron; vemolate; xylachlor; and salts, esters, optically active isomers, and mixtures thereof.

In some aspects, the additional pesticide or an agriculturally acceptable salt or ester thereof is provided in a premixed formulation with (a), (b), or combinations thereof. In some aspects, the pyridine carboxylate herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof is provided in a premixed formulation with an additional pesticide. In some aspects, the cloquintocet safener or an agriculturally acceptable salt or ester thereof is provided in a premixed formulation with an additional pesticide.

In some aspects, the safened compositions may include one or more herbicidal active ingredients in addition to (a). In some aspects, the safened compositions do not include an herbicidal active ingredient in addition to (a). In some aspects, the safened compositions may exclude one or more herbicidal active ingredients specified above. In some aspects, the safened compositions may include one or more herbicidal active ingredients in addition to (a), but may exclude one or more herbicidal ingredients specified above. In some aspects, the safened compositions may include one or more safeners in addition to (b). In some aspects, the safened compositions do not include a safener in addition to (b). In some aspects, the composition may include other components, such as adjuvants, but does not include a herbicidal active ingredient in addition to (a) or a safener in addition to (b).

2. Adjuvants

In some aspects, the additive includes an agriculturally acceptable adjuvant. Exemplary agriculturally acceptable adjuvants include, but are not limited to, antifreeze agents, antifoam agents, compatibilizing agents, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, colorants, odorants, penetration aids, wetting agents, spreading agents, dispersing agents, thickening agents, freeze point depressants, antimicrobial agents, crop oil, adhesives (for instance, for use in seed formulations), surfactants, protective colloids, emulsifiers, tackifiers, and mixtures thereof.

Exemplary agriculturally acceptable adjuvants include, but are not limited to, crop oil concentrates (e.g., 85% mineral oil+15% emulsifiers); nonylphenol ethoxylates; benzylcocoalkyl-dimethyl quatemary ammonium salts; blends of petroleum hydrocarbon, alkyl esters, organic acids, and anionic surfactants; C₉-C₁₁ alkylpolyglycoside; phosphate alcohol ethoxylates; natural primary alcohol (C₁₂-C₁₆) ethoxylate; di-sec-butylphenol EO-PO block copolymers; polysiloxane-methyl cap; nonylphenol ethoxylate+urea ammonium nitrates; emulsified methylated seed oils; tridecyl alcohol (synthetic) ethoxylates (e.g., 8 EO); tallow amine ethoxylates (e.g., 15 EO); and PEG(400) dioleate-99.

Exemplary surfactants (e.g., wetting agents, tackifiers, dispersants, emulsifiers) include, but are not limited to: the alkali metal salts, alkaline earth metal salts and ammonium salts of fatty acids or of aromatic sulfonic acids (e.g., lignosulfonic acids, phenolsulfonic acids, naphthalenesulfonic acids, and dibutylnaphthalenesulfonic acid); alkyl- and alkylarylsulfonates; alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates; salts of sulfated hexa-, hepta- and octadecanols; salts of fatty alcohol glycol ethers; condensates of sulfonated naphthalene and its derivatives with formaldehyde; condensates of naphthalene or of the naphthalene sulfonic acids with phenol and formaldehyde; polyoxyethylene octylphenol ether; ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl or tributylphenyl polyglycol ether; alkyl aryl polyether alcohols; isotridecyl alcohol; fatty alcohol/ethylene oxide condensates; ethoxylated castor oil; polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers; lauryl alcohol polyglycol ether acetate; sorbitol esters; lignosulfite waste liquors and proteins; denatured proteins, polysaccharides (e.g., methylcellulose); hydrophobically modified starches; and polyvinyl alcohols, polycarboxylates, polyalkoxylates, polyvinyl amines, polyethyleneimine, polyvinylpyrrolidone, and copolymers thereof.

Exemplary thickeners include, but are not limited to, polysaccharides (e.g., xanthan gum), organic and inorganic sheet minerals, and mixtures thereof.

Exemplary antifoam agents include, but are not limited to, silicone emulsions, long-chain alcohols, fatty acids, fatty acid salts, organofluorine compounds, and mixtures thereof.

Exemplary antimicrobial agents include, but are not limited to: bactericides based on dichlorophen and benzyl alcohol hemiformal; isothiazolinone derivatives, such as alkylisothiazolinones and benzisothiazolinones; and mixtures thereof.

Exemplary antifreeze agents, include, but are not limited to ethylene glycol, propylene glycol, urea, glycerol, and mixtures thereof.

Exemplary colorants include, but are not limited to, the dyes known under the names Rhodamine B, pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108, and mixtures thereof.

Exemplary adhesives include, but are not limited to, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, tylose, and mixtures thereof.

3. Carriers

In some aspects, the additive includes a carrier. In some aspects, the additive includes a liquid or solid carrier. In some aspects, the additive includes an organic or inorganic carrier. Exemplary liquid carriers include, but are not limited to: water; petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; esters of monoalcohols or dihydric, trihydric, or other lower polyalcohols (4-6 hydroxy containing), such as 2-ethyl hexyl stearate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate, di-octyl succinate, di-butyl adipate, di-octyl phthalate and the like; esters of mono, di and polycarboxylic acids and the like; toluene; xylene; petroleum naphtha; crop oil; acetone; methyl ethyl ketone; cyclohexanone; trichloroethylene; perchloroethylene; ethyl acetate; amyl acetate; butyl acetate; propylene glycol monomethyl ether and diethylene glycol monomethyl ether; methyl alcohol; ethyl alcohol; isopropyl alcohol; amyl alcohol; ethylene glycol; propylene glycol; glycerin; N-methyl-2-pyrrolidinone; N;N-dimethyl alkylamides; dimethyl sulfoxide; and liquid fertilizers, as well as mixtures thereof. Exemplary solid carriers include, but are not limited to: silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, pyrophyllite clay, attapulgus clay, kieselguhr, calcium carbonate, bentonite clay, Fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, and mixtures thereof.

B. Physical States

In some aspects, the formulation of (a) the pyridine carboxylate herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof and (b) the cloquintocet safener or an agriculturally acceptable salt or ester thereof may be present in suspended, emulsified, dissolved, or solid form. Exemplary formulations include, but are not limited to, aqueous solutions, aqueous suspensions, aqueous dispersions, aqueous emulsions, aqueous microemulsions, aqueous suspo-emulsions, oil solutions, oil suspensions, oil dispersions, oil emulsions, oil microemulsions, oil suspo-emulsions, self-emulsifying formulations, pastes, powders, dusts, granules, and materials for spreading.

In some aspects, (a) and (b) are aqueous solutions that can be diluted before use. In various aspects, (a) and (b) are provided as a high-strength formulation such as a concentrate. In some aspects, concentrates suitable for dilution with water can be prepared, comprising (a), (b), a wetting agent, a tackifier, and a dispersant or emulsifier. In some aspects, the concentrate is stable and retains potency during storage and shipping. In various aspects, the concentrate is a clear, homogeneous liquid that is stable at temperatures of 54° C. or greater. In some aspects, the concentrate does not exhibit any precipitation of solids at temperatures of −10° C. or higher. In some aspects, the concentrate does not exhibit separation, precipitation, or crystallization of any components at low temperatures. For example, the concentrate remains a clear solution at temperatures below 0° C. (e.g., below −5° C., below −10° C., below −15° C.). In some aspects, the concentrate exhibits a viscosity of less than 50 centipoise (50 megapascals), even at temperatures as low as 5° C. In some aspects, the concentrate does not exhibit separation, precipitation, or crystallization of any components during storage for a period of 2 weeks or greater (e.g., 4 weeks, 6 weeks, 8 weeks, 3 months, 6 months, 9 months, or 12 months or greater).

In some aspects, emulsions, pastes, or oil dispersions can be prepared by homogenizing (a) and (b) in water with a wetting agent, tackifier, dispersant, or emulsifier. In some aspects, concentrates suitable for dilution with water can be prepared, comprising (a), (b), a wetting agent, a tackifier, and a dispersant or emulsifier.

In some aspects, powders, materials for spreading, or dusts can be prepared by mixing or concomitant grinding of (a) and (b) and optionally other additives with a solid carrier.

In some aspects, granules (e.g., coated granules, impregnated granules and homogeneous granules) can be prepared by binding the (a) and (b) to solid carriers.

In some aspects, the formulations comprise from 1% to 99% of (a) and 1% to 99% of (b) (e.g., 95% of (a) and 5% of (b); 70% of (a) and 30% of (b); or 30% of (a) and 70% of (b)) by total weight of (a) and (b). In formulations designed to be employed as concentrates, the total amount of (a) and (b) can be present in a concentration of from about 0.1 to about 98 weight percent (wt. %), based on the total weight of the formulation. For example, the total amount of (a) and (b) can be present in a concentration as little as about 1 wt. %, about 2.5 wt. %, about 5 wt. %, about 7.5 wt. %, about 10 wt. %, about 15 wt. %, about 20 wt. %, about 25 wt. %, about 30 wt. %, about 35 wt. %, about 40 wt. %, about 45 wt. %, as high as about 50 wt. %, about 55 wt. %, about 60 wt. %, about 65 wt. %, about 70 wt. %, about 75 wt. %, about 80 wt. %, about 85 wt. %, about 90 wt. %, about 95 wt. %, about 97 wt. %, or within any range defined between any two of the forgoing values, such as between about 1 wt. % to about 97 wt. %, between about 10 wt. % to about 90 wt. %, between about 20 wt. % to about 45 wt. %, and about 25 wt. % to about 50 wt. % based on the total weight of the formulation. Concentrates can be diluted with an inert carrier, such as water, prior to application. The diluted formulations applied to undesirable vegetation or the locus of undesirable vegetation can contain from 0.0006 to 8.0 wt. % of the total amount of (a) and (b) (e.g., from 0.001 to 5.0 wt. %), based on the total weight of the diluted formulation.

C. Packaging

In some aspects, the formulation can be in the form of a single package formulation including both: (a) the pyridine carboxylate herbicide or an agriculturally acceptable N-oxide, salt, or ester thereof; and (b) the cloquintocet safener or an agriculturally acceptable salt or ester thereof. In some aspects, the formulation can be in the form of a single package formulation including both (a) and (b) and further including at least one additive. In some aspects, the formulation can be in the form of a multi-package formulation, such as a two-package formulation, wherein one package contains (a) and optionally at least one additive while the other package contains (b) and optionally at least one additive. In some aspects of the two-package formulation, the formulation including (a) and optionally at least one additive and the formulation including (b) and optionally at least one additive are mixed before application and then applied simultaneously. In some aspects, the mixing is performed as a tank mix (e.g., the formulations are mixed immediately before or upon dilution with water). In some aspects, the formulation including (a) and the formulation including (b) are not mixed but are applied sequentially (in succession), for example, immediately or within 1 hour, within 2 hours, within 4 hours, within 8 hours, within 16 hours, within 24 hours, within 2 days, or within 3 days, of each other.

VI. Methods of Use

The compositions disclosed herein can be applied in any known technique for applying herbicides. Exemplary application techniques include, but are not limited to, spraying, atomizing, dusting, spreading, or direct application into water. The method of application can vary depending on the intended purpose. In some aspects, the method of application can be chosen to ensure the finest possible distribution of the compositions disclosed herein.

In some aspects, a method of controlling undesirable vegetation which comprises contacting the vegetation or the locus thereof with or applying to the soil or water to prevent the emergence or growth of vegetation any of the compositions is disclosed herein.

The compositions disclosed herein can be applied pre-emergence (before the emergence of undesirable vegetation) or post-emergence (e.g., during or after emergence of the undesirable vegetation). In some aspects, the composition is applied post-emergence to the undesirable vegetation. In some aspects, the pyridine carboxylate herbicide and cloquintocet safener are applied simultaneously. In some aspects, the pyridine carboxylate herbicide and cloquintocet safener are applied sequentially, for example, immediately or with minimal delay, within about 10 minutes, within about 20 minutes, within about 30 minutes, within about 40 minutes, within about 1 hour, within about 2 hours, within about 4 hours, within about 8 hours, within about 16 hours, within about 24 hours, within about 2 days, or within about 3 days, of each other. In some aspects, the pyridine carboxylate herbicide can be applied pre-emergently or post-emergently to the undesirable vegetation and the cloquintocet safener can be applied as a seed treatment to the crop seeds. When applied as a seed treatment, the cloquintocet safener is applied at rate from 0.01 to 10 g ai of safener per kg (g ai/kg) of crop seed, preferably 0.05 to 1 g ai/kg of crop seed, in particular 0.1 to 0.5 g ai/kg of crop seed. If solutions of safeners are used to treat the seeds, the concentration of the safener in the solution is, for example, from 1 to 10000 ppm, preferably 100 to 1000 ppm, based on weight.

When the compositions are used in crops, the compositions can be applied after seeding and before or after the emergence of the crop plants. In some aspects, the compositions disclosed herein show good crop tolerance even when the crop has already emerged and can be applied during or after the emergence of the crop plants. In some aspects, when the compositions are used in crops, the compositions can be applied before seeding of the crop plants.

In some aspects, the compositions disclosed herein are applied to vegetation or an area adjacent the vegetation or applying to soil or water to prevent the emergence or growth of vegetation by spraying (e.g., foliar spraying). In some aspects, the spraying techniques use, for example, water as carrier and spray volume rates of from 2 liters per hectare (L/ha) to 2000 L/ha (e.g., from 10-1000 L/ha or from 50-500 L/ha). In some aspects, the compositions disclosed herein are applied by the low-volume or the ultra-low-volume method, wherein the application is in the form of micro granules. In some aspects, wherein the compositions disclosed herein are less well tolerated by certain crop plants, the compositions can be applied with the aid of the spray apparatus in such a way that they come into little contact, if any, with the leaves of the sensitive crop plants while reaching the leaves of undesirable vegetation that grows underneath or on the bare soil (e.g., post-directed or lay-by). In some aspects, the compositions disclosed herein can be applied as dry formulations (e.g., granules, powders, or dusts).

In some aspects, wherein the undesirable vegetation is treated post-emergence, the compositions disclosed herein are applied by foliar application. In some aspects, herbicidal activity is exhibited by the compounds of the mixture when they are applied directly to the plant or to the locus of the plant at any stage of growth or before planting or emergence. The effect observed can depend upon the type of undesirable vegetation to be controlled, the stage of growth of the undesirable vegetation, the application parameters of dilution and spray drop size, the particle size of solid components, the environmental conditions at the time of use, the specific compound employed, the specific adjuvants and carriers employed, the soil type, and the like, as well as the amount of chemical applied. In some aspects, these and other factors can be adjusted to promote non-selective or selective herbicidal action.

The compositions and methods disclosed herein can be used to control undesirable vegetation in a variety of applications. The compositions and methods disclosed herein can be used for controlling undesirable vegetation in areas including, but not limited to, farmland, turfgrass, pastures, grasslands, rangelands, fallow land, rights-of-way, aquatic settings, tree and vine, wildlife management areas, or rangeland. In some aspects, the undesirable vegetation is controlled in a row crop. Exemplary crops include, but are not limited to, wheat, barley, triticale, rye, teff, oats, maize, cotton, soy, sorghum, rice, millet, sugarcane and range land (e.g., pasture grasses). In some aspects, the compositions and methods disclosed herein can be used for controlling undesirable vegetation in maize, wheat, barley, rice, sorghum, millet, or oats or combinations thereof. In some aspects, the compositions and methods disclosed herein can be used for controlling undesirable vegetation in broadleaf crops. In some aspects, the compositions and methods disclosed herein can be used for controlling undesirable vegetation in canola, flax, sunflower, soy, or cotton. In some aspects, the compositions and methods disclosed herein can be used in industrial vegetation management (IVM) or for utility, pipeline, roadside, and railroad rights-of-way applications. In some aspects, the compositions and methods disclosed herein can also be used in forestry (e.g., for site preparation or for combating undesirable vegetation in plantation forests). In some aspects, the compositions and methods disclosed herein can be used to control undesirable vegetation in conservation reserve program lands (CRP), trees, vines, grasslands, and grasses grown for seeds. In some aspects, the compositions and methods disclosed herein can be used on lawns (e.g., residential, industrial, and institutional), golf courses, parks, cemeteries, athletic fields, and sod farms.

The compositions and methods disclosed herein can also be used in crop plants that are resistant to, for instance, herbicides, pathogens, or insects. In some aspects, the compositions and methods disclosed herein can be used in crop plants that are resistant to one or more herbicides because of genetic engineering or breeding. In some aspects, the compositions and methods disclosed herein can be used in crop plants that are resistant to one or more pathogens such as plant pathogenic fungi owing to genetic engineering or breeding. In some aspects, the compositions and methods disclosed herein can be used in crop plants that are resistant to attack by insects owing to genetic engineering or breeding. Exemplary resistant crops include, but are not limited to, crops that are resistant to photosystem II inhibitors, or crop plants that, owing to introduction of the gene for Bacillus thuringiensis (or Bt) toxin by genetic modification, are resistant to attack by certain insects. In some aspects, the compositions and methods described herein can be used in conjunction with glyphosate, glufosinate, dicamba, phenoxy auxins, pyridyloxy auxins, aryloxyphenoxypropionates, acetyl CoA carboxylase (ACCase) inhibitors, imidazolinones, acetolactate synthase (ALS) inhibitors, 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, protoporphyrinogen oxidase (PPO) inhibitors, triazines, and bromoxynil to control vegetation in crops tolerant to glyphosate, glufosinate, dicamba, phenoxy auxins, pyridyloxy auxins, aryloxyphenoxypropionates, ACCase inhibitors, imidazolinones, ALS inhibitors, HPPD inhibitors, PPO inhibitors, triazines, bromoxynil, or combinations thereof. In some aspects, the undesirable vegetation is controlled in glyphosate, glufosinate, dicamba, phenoxy auxins, pyridyloxy auxins, aryloxyphenoxypropionates, ACCase inhibitors, ALS inhibitors, HPPD inhibitors, PPO inhibitors, triazines, and bromoxynil tolerant crops possessing single, multiple or stacked traits conferring tolerance to single or multiple chemistries or multiple modes of action. In some aspects, the undesirable vegetation can be controlled in a crop that is ACCase-tolerant, ALS-tolerant, or a combination thereof. The combination of (a) and (b) can be used in combination with one or more herbicides that are selective for the crop being treated and which complement the spectrum of weeds controlled by these compounds at the application rate employed. In some aspects, the compositions described herein and other complementary herbicides are applied at the same time, either as a combination formulation or as a tank mix, or as sequential applications. The compositions and methods may be used in controlling undesirable vegetation in crops possessing agronomic stress tolerance (including but not limited to drought, cold, heat, salt, water, nutrient, fertility, pH), pest tolerance (including but not limited to insects, fungi and pathogens), and crop improvement traits (including but not limited to yield; protein, carbohydrate, or oil content; protein, carbohydrate, or oil composition; plant stature and plant architecture).

In some aspects, the compositions disclosed herein can be used for controlling undesirable vegetation including grasses, broadleaf weeds, sedge weeds, and combinations thereof. In some aspects, the compositions disclosed herein can be used for controlling undesirable vegetation including, but not limited to, Polygonum species, Amaranthus species, Chenopodium species, Sida species, Ambrosia species, Cyperus species, Setaria species, Sorghum species, Acanthospermum species, Anthemis species, Atriplex species, Brassica species, Cirsium species, Convolvulus species, Conyza species, Cassia species, Commelina species, Datura species, Euphorbia species, Geranium species, Galinsoga species, Ipomea species, Lamium species, Lolium species, Malva species, Matricaria species, Prosopis species, Rumex species, Sisymbrium species, Solanum species, Trifolium species, Xanthium species, Veronica species, and Viola species. In some aspects, the undesired vegetation includes common chickweed (Stellaria media), velvetleaf (Abutilon theophrasti), hemp sesbania (Sesbania exaltata Cory), Anoda cristata, Bidens pilosa, Brassica kaber, shepherd's purse (Capsella bursa-pastoris), cornflower (Centaurea cyanus or Cyanus segetum), hempnettle (Galeopsis tetrahit), cleavers (Galium aparine), common sunflower (Helianthus annuus), Desmodium tortuosum, Italian ryegrass (Lolium multiflorum), kochia (Kochia scoparia), Medicago arabica, Mercurialis annua, Myosotis arvensis, common poppy (Papaver rhoeas), Raphanus raphanistrum, broad-leaf dock (Rumex obtusifolius), Russian thistle (Salsola kali), wild mustard (Sinapis arvensis), Sonchus arvensis, Thlaspi arvense, Tagetes minuta, Richardia brasiliensis, Plantago major, Plantago lanceolata, bird's-eye speedwell (Veronica persica), pigweed (Amaranthus retroflexus), winter rape (Brassica napus), lambsquarters (Chenopodium album), Canada thistle (Cirsium arvense), nutsedge (Cyperus esculentus), poinsettia (Euphorbiaheterophylla), prickly lettuce (Lactuca serriola), purple deadnettle (Lamium purpureum), wild chamomile (Matricaria chamomilla), false chamomile (Matricaria inodora), field chamomile (Anthemis arvensis), common buckwheat (Fagopyrum esculentum), wild buckwheat (Polygonum convulvus), giant foxtail (Setaria faberi), green foxtail (Setaria viridis), common sorghum (Sorghum vulgare), wild pansy (Viola tricolor), blackgrass (Alopecurus myosuroides), wild oat (Avena fatua), large crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloa crus-galli), Canada horseweed (Erigeron canadensis), volunteer soybean (Glycine max), ivyleaf morningglory (Ipomoea hederacea), Chinese sprangletop (Leptochloa chinensis), and Johnson grass (SORHA, Sorghum halepense), or combinations thereof.

The compositions described herein can be used to control herbicide resistant or tolerant weeds. The methods employing the compositions described herein may also be employed to control herbicide resistant or tolerant weeds. Exemplary resistant or tolerant weeds include, but are not limited to, biotypes resistant or tolerant to acetolactate synthase (ALS) or acetohydroxy acid synthase (AHAS) inhibitors (e.g., imidazolinones, sulfonylureas, pyrimidinylthiobenzoates, triazolopyrimidines, sulfonylaminocarbonyl-triazolinones), photosystem II inhibitors (e.g., phenylcarbamates, pyridazinones, triazines, triazinones, uracils, amides, ureas, benzothiadiazinones, nitriles, phenylpyridazines), acetyl CoA carboxylase (ACCase) inhibitors (e.g., aryloxyphenoxypropionates, cyclohexanediones, phenylpyrazolines), synthetic auxins (e.g., benzoic acids, phenoxycarboxylic acids, pyridine carboxylates, quinoline carboxylic acids), auxin transport inhibitors (e.g., phthalamates, semicarbazones), photosystem I inhibitors (e.g., bipyridyliums), 5-enolpyruvylshikimate-3-phosphate (EPSP) synthase inhibitors (e.g., glyphosate), glutamine synthetase inhibitors (e.g., glufosinate, bialafos), microtubule assembly inhibitors (e.g., benzamides, benzoic acids, dinitroanilines, phosphoramidates, pyridines), mitosis inhibitors (e.g., carbamates), very long chain fatty acid (VLCFA) inhibitors (e.g., acetamides, chloroacetamides, oxyacetamides, tetrazolinones), fatty acid and lipid synthesis inhibitors (e.g., phosphorodithioates, thiocarbamates, benzofuranes, chlorocarbonic acids), protoporphyrinogen oxidase (PPO) inhibitors (e.g., diphenylethers, N-phenylphthalimides, oxadiazoles, oxazolidinediones, phenylpyrazoles, pyrimidindiones, thiadiazoles, triazolinones), carotenoid biosynthesis inhibitors (e.g., clomazone, amitrole, aclonifen), phytoene desaturase (PDS) inhibitors (e.g., amides, anilidex, furanones, phenoxybutan-amides, pyridiazinones, pyridines), 4-hydroxyphenyl-pyruvate-dioxygenase (HPPD) inhibitors (e.g., callistemones, isoxazoles, pyrazoles, triketones), cellulose biosynthesis inhibitors (e.g., nitriles, benzamides, quinclorac, triazolocarboxamides), herbicides with multiple modes of action such as quinclorac, and unclassified herbicides such as arylaminopropionic acids, difenzoquat, endothall, and organoarsenicals. Exemplary resistant or tolerant weeds include, but are not limited to, biotypes with resistance or tolerance to multiple herbicides, biotypes with resistance or tolerance to multiple chemical classes, biotypes with resistance or tolerance to multiple herbicide modes of action, and biotypes with multiple resistance or tolerance mechanisms (e.g., target site resistance or metabolic resistance).

By way of non-limiting illustration, examples of certain aspects of the present disclosure are given below. Parts and percentages are on a per weight basis unless otherwise indicated.

EXAMPLES Greenhouse Trial Methodology—Evaluation of Postemergence Herbicidal Safening in Crops

Seeds of the desired test plant species were planted in a 90:10% v/v (volume/volume) mixture of PRO-MIX® BX (Premier Tech Horticulture, Quakertown, Pa., USA) and PROFILE® GREENS GRADE™ (Profile Products LLC, Buffalo Grove, Ill., USA) planting mixture, which typically has a pH of 5.2 to 6.2 and an organic matter content of at least 50 percent, in plastic pots with a surface area of 103.2 square centimeters (cm²). When required to ensure good germination and healthy plants, a fungicide treatment and/or other chemical or physical treatment was applied. The plants were grown for 7-36 days (d) in a greenhouse with an approximate 14-hour (h) photoperiod which was maintained at about 23° C. during the day and 22° C. during the night. Nutrients and water were added on a regular basis and supplemental lighting was provided with overhead metal halide 1000-Watt lamps as necessary. The plants were employed for testing when they reached the second or third true leaf stage.

Emulsifiable concentrates of each of each pyridine carboxylate herbicide (Compound A or Compound B) were prepared at 100 grams acid equivalent per liter (g ae/L). An aliquot of each emulsifiable concentrate was placed in a 25 mL glass vial and diluted with an aqueous mixture of 1.25% (v/v) ACTIROB® B esterified rapeseed oil (Bayer Crop Science, Research Triangle Park, N.C., USA) or MSO® Concentrate with LECI-TECH® methylated soybean oil (Loveland Products, Loveland, Colo., USA) to obtain concentrated stock solutions at the highest application rate for each herbicide, based upon a 12 milliliter (mL) application volume at a rate of 187 liters per hectare (L/ha). The concentrated stock solutions were further diluted with an aqueous mixture of 1.25% v/v ACTIROB® B or MSO® Concentrate with LECI-TECH® to obtain stock solutions at reduced application rates for each herbicide. Spray solutions of the herbicide combinations (Compound A or Compound B plus safener) were prepared by adding weighed amounts or aliquots of the safener to the stock solutions of Compound A or Compound B to form 12-mL spray solutions in two-way combinations.

The spray solutions were applied to the plant material with an overhead Mandel track sprayer equipped with 8002E nozzles calibrated to deliver 187 L/ha over an application area of 0.503 square meters (m²) at a spray height of 18 inches (43 centimeters (cm)) above the average plant canopy. Control plants were sprayed in the same manner with the solvent blank. All herbicide (component a) application rates are given as “g ae/ha” and all safener (component b) application rates are given as “g ai/ha.”

The treated plants and control plants were placed in a greenhouse as described above and watered by sub-irrigation to prevent wash-off of the test compounds. After 20-22 d, the condition of the test plants as compared with that of the control plants was determined visually and scored on a scale of 0 to 100 percent where 0 corresponds to no injury and 100 corresponds to complete kill.

The details of the safened compositions and the crops tested are specified in the following Examples.

Example 1

A safened composition comprising cloquintocet-acid (CQC-a) and Compound A was tested on spring wheat (TRZAS), winter wheat (TRZAW), durum wheat (TRZDU), spring barley (HORVS), winter barley (HORVW), and common oats (AVESA), and the phytotoxicity of the safened composition on each crop was measured. In addition, the efficacy of the safened compositions on undesirable vegetation, including field chamomile (ANTAR, Anthemis arvensis), winter rape (BRSNW, Brassica napus), false chamomile (MATIN, Matricaria inodora), and wild mustard (SINAR, Sinapis arvensis), was measured.

The results are summarized in Tables 1-4 below.

TABLE 1 Safening of Effects (% visual injury) of Cloquintocet-acid (CQC-a) and Compound A on grain crops. Application Compound A 40 0 40 rate (g/ha) CQC-a 0 40 40 Herbicide: 1:1 Safener Ratio TRZAS Ob 45 0 0 Ex — — 45 Δ −45 TRZAW Ob 35 0 5 Ex — — 35 Δ 0 0 −30 TRZDU Ob 45 0 0 Ex — — 45 Δ −45 HORVS Ob 20 0 5 Ex — — 20 Δ −15 HORVW Ob 40 0 10 Ex — — 40 Δ −10 AVESA Ob 0 0 0 Ex — — 0 Δ 0 g/ha = grams per hectare TRZAS = Triticum aestivum (spring wheat) TRZAW = Triticum aestivum (winter wheat) TRZDU = Triticum aestivum (durum wheat) HORVS = Hordeum vulgare (spring barley) HORVW = Hordeum vulgare (winter barley) AVESA = Avena sativa (common oat)

TABLE 2 Safening of Effects (% visual injury) of Cloquintocet-acid (CQC-a) and Compound A on grain crops and weeds. Appli- Compound 40 0 0 0 0 40 40 40 40 cation rate A (g/ha) CQC-a 0 10 20 40 80 10 20 40 80 Herbicide: 4:1 2:1 1:1 1:2 Safener Ratio TRZAS Ob 40 0 0 0 0 0 0 0 0 Ex — — — — — 40 40 40 40 Δ −40 −40 −40 −40 TRZAW Ob 35 0 0 0 0 0 0 0 0 Ex — — — — — 35 35 35 35 Δ −35 −35 −35 −35 HORVS Ob 40 0 0 0 0 10 10 0 0 Ex — — — — — 40 40 40 40 Δ −30 −30 −40 −40 HORVW Ob 30 0 0 0 0 5 0 0 0 Ex — — — — — 30 30 30 30 Δ −25 −30 −30 −30 MATIN Ob 100 0 0 0 0 97 99 99 97 Ex — — — — — 100 100 100 100 Δ −3 −2 −2 −3 SINAR Ob 99 0 0 0 0 100 99 97 100 Ex — — — — — 99 99 99 99 Δ 2 0 −2 2 g/ha = grams per hectare TRZAS = Triticum aestivum (spring wheat) TRZAW = Triticum aestivum (winter wheat) HORVS = Hordeum vulgare (spring barley) HORVW = Hordeum vulgare (winter barley) MATIN = Matricaria inodora (false chamomile) SINAR = Sinapis arvensis (wild mustard)

TABLE 3 Safening of Effects (% visual injury) of Cloquintocet-acid (CQC-a) and Compound A on grain crops. Appli- Compound 40 0 0 0 0 40 40 40 40 cation rate A (g/ha) CQC-a 0 20 40 80 120 20 40 80 120 Herbicide: 2:1 1:1 1:2 1:3 Safener Ratio TRZAS Ob 23 0 0 0 0 0 0 0 0 Ex — — — — — 23 23 23 23 Δ −23 −23 −23 −23 TRZAW Ob 25 0 0 0 0 3 3 2 0 Ex — — — — — 25 25 25 25 Δ −22 −22 −23 −25 HORVS Ob 17 0 0 0 0 0 0 0 0 Ex — — — — — 17 17 17 17 Δ −17 −17 −17 −17 g/ha = grams per hectare TRZAS = Triticum aestivum (spring wheat) TRZAW = Triticum aestivum (winter wheat) HORVS = Hordeum vulgare (spring barley)

TABLE 4 Safening of Effects (% visual injury) of Cloquintocet-acid (CQC-a) and Compound A on grain crops and weeds. Appli- Compound 20 0 0 0 0 20 20 20 20 cation rate A (g/ha) CQC-a 0 5 10 20 40 5 10 20 40 Herbicide: 4:1 2:1 1:1 1:2 Safener Ratio TRZAS Ob 15 0 0 0 0 0 0 0 0 Ex — — — — — 15 15 15 15 Δ −15 −15 −15 −15 TRZAW Ob 20 0 0 0 0 5 7 7 0 Ex — — — — — 20 20 20 20 Δ −15 −13 −13 −20 HORVS Ob 20 0 0 0 0 10 0 0 0 Ex — — — — — 20 20 20 20 Δ −10 −20 −20 −20 HORVW Ob 15 0 0 0 0 0 0 0 0 Ex — — — — — 15 15 15 15 Δ −15 −15 −15 −15 ANTAR Ob 95 0 0 0 0 90 95 100 80 Ex — — — — — 95 95 95 95 Δ −5 0 5 −15 BRSNW Ob 70 0 0 0 0 70 75 85 85 Ex — — — — — 70 70 70 70 Δ 0 5 15 15 g/ha = grams per hectare TRZAS = Triticum aestivum (spring wheat) TRZAW = Triticum aestivum (winter wheat) HORVS = Hordeum vulgare (spring barley) HORVW = Hordeum vulgare (winter barley) ANTAR = Anthemis arvensis (field chamomile) BRSNW = Brassica napus (winter rape)

Example 2

A safened composition comprising cloquintocet-dimethylammonium salt (CQC-DMA) and Compound A was tested on spring barley (HORVS), winter wheat (TRZAW), winter barley (HORVW), spring wheat (TRZAS), durum wheat (TRZDU), and common oats (AVESA), and the phytotoxicity of the safened composition on each crop was measured. In addition, the efficacy of the safened compositions on undesirable vegetation, including wild chamomile (MATCH, Matricaria chamomilla), Russian thistle (SASKR, Salsola kali), and winter rape (BRSNW, Brassica napus), was measured.

The results are summarized in Tables 5-6 below.

TABLE 5 Safening of Effects (% visual injury) of Cloquintocet- dimethylammonium salt (CQC-DMA) and Compound A on grain crops. Application Compound A 40 0 40 rate (g/ha) CQC-DMA 0 40 40 Herbicide: 1:1 Safener Ratio HORVS Ob 20 0 0 Ex — — 20 Δ −20 TRZAW Ob 35 0 5 Ex — — 35 Δ 0 0 −30 HORVW Ob 40 0 10 Ex — — 40 Δ −30 TRZAS Ob 45 0 0 Ex — — 45 Δ −45 TRZDU Ob 45 0 0 Ex — — 45 Δ −45 AVESA Ob 0 0 0 Ex — — 0 Δ 0 g/ha = grams per hectare HORVS = Hordeum vulgare (spring barley) TRZAW = Triticum aestivum (winter wheat) HORVW = Hordeum vulgare (winter barley) TRZAS = Triticum aestivum (spring wheat) TRZDU = Triticum aestivum (durum wheat) AVESA = Avena sativa (common oat)

TABLE 6 Safening of Effects (% visual injury) of Cloquintocet- dimethylammonium salt (CQC-DMA) and Compound A on grain crops and weeds. Application Compound A 20 0 0 0 20 20 20 rate (g/ha) CQC-DMA 0 10 20 40 10 20 40 Herbicide: 2:1 1:1 1:2 Safener Ratio HORVS Ob 0 0 0 0 0 0 0 Ex — — — — 0 0 0 Δ 0 0 0 TRZAS Ob 25 0 0 0 0 0 0 Ex — — — — 25 25 25 Δ −25 −25 −25 MATCH Ob 50 0 0 0 65 50 Ex — — — — 50 50 Δ 15 0 SASKR Ob 60 0 0 0 60 60 Ex — — — — 60 60 Δ 0 0 BRSNW Ob 95 0 0 0 100 95 Ex — — — — 95 95 Δ 5 0 g/ha = grams per hectare HORVS = Hordeum vulgare (spring barley) TRZAS = Triticum aestivum (spring wheat) MATCH = Matricaria chamomilla (wild chamomile) SASKR = Salsola kali (Russian thistle) BRSNW = Brassica napus (winter rape)

Example 3

A safened composition comprising cloquintocet-triethylamine salt (CQC-TEA) and Compound A was tested on spring barley (HORVS), winter barley (HORVW), spring wheat (TRZAS), winter wheat (TRZAW), durum wheat (TRZDU), and common oats (AVESA), and the phytotoxicity of the safened composition on each crop was measured. In addition, the efficacy of the safened compositions on undesirable vegetation, including wild chamomile (MATCH, Matricaria chamomilla), Russian thistle (SASKR, Salsola kali), and winter rape (BRSNW, Brassica napus), was measured.

The results are summarized in Tables 7-8 below.

TABLE 7 Safening of Effects (% visual injury) of Cloquintocet- triethylamine salt (CQC-TEA) and Compound A on grain crops. Application Compound A 40 0 40 rate (g/ha) CQC-TEA 0 40 40 Herbicide: 1:1 Safener Ratio HORVS Ob 20 0 3 Ex — — 20 Δ −18 HORVW Ob 40 0 5 Ex — — 40 Δ 0 0 −35 TRZAS Ob 45 0 0 Ex — — 45 Δ −45 TRZAW Ob 35 0 10 Ex — — 35 Δ −25 TRZDU Ob 45 0 0 Ex — — 45 Δ −45 AVESA Ob 0 0 0 Ex — — 0 Δ 0 g/ha = grams per hectare HORVS = Hordeum vulgare (spring barley) HORVW = Hordeum vulgare (winter barley) TRZAS = Triticum aestivum (spring wheat) TRZAW = Triticum aestivum (winter wheat) TRZDU = Triticum aestivum (durum wheat) AVESA = Avena sativa (common oat)

TABLE 8 Safening of Effects (% visual injury) of Cloquintocet-triethylamine salt (CQC-TEA) and Compound A on grain crops and weeds. Application Compound A 20 0 0 0 20 20 20 rate (g/ha) CQC-TEA 0 10 20 40 10 20 40 Herbicide: 2:1 1:1 1:2 Safener Ratio HORVS Ob 0 0 0 0 0 0 0 Ex — — — — 0 0 0 Δ 0 0 0 TRZAS Ob 25 0 0 0 0 0 0 Ex — — — — 25 25 25 Δ −25 −25 −25 MATCH Ob 50 0 0 0 65 60 Ex — — — — 50 50 Δ 15 10 SASKR Ob 60 0 0 0 60 60 Ex — — — — 60 60 Δ 0 0 BRSNW Ob 95 0 0 0 80 90 Ex — — — — 95 95 Δ −15 −5 g/ha = grams per hectare HORVS = Hordeum vulgare (spring barley) TRZAS = Triticum aestivum (spring wheat) MATCH = Matricaria chamomilla (wild chamomile) SASKR = Salsola kali (Russian thistle) BRSNW = Brassica napus (winter rape)

Example 4

A safened composition comprising cloquintocet-triethylamine salt (CQC-TEA) and Compound B was tested on spring barley (HORVS), winter barley (HORVW), spring wheat (TRZAS), winter wheat (TRZAW), durum wheat (TRZDU), and common oats (AVESA), and the phytotoxicity of the safened composition on each crop was measured.

The results are summarized in Table 9 below.

TABLE 9 Safening of Effects (% visual injury) of Cloquintocet- triethylamine salt (CQC-TEA) and Compound B on grain crops. Application Compound B 40 0 40 rate (g/ha) CQC-TEA 0 40 40 Herbicide: 1:1 Safener Ratio HORVS Ob 25 0 8 Ex — — 25 Δ −18 HORVW Ob 38 0 8 Ex — — 38 Δ 0 0 −30 TRZAS Ob 48 0 5 Ex — — 48 Δ −43 TRZAW Ob 50 0 13 Ex — — 50 Δ −38 TRZDU Ob 40 0 0 Ex — — 40 Δ −40 AVESA Ob 0 0 0 Ex — — 0 Δ 0 g/ha = grams per hectare HORVS = Hordeum vulgare (spring barley) HORVW = Hordeum vulgare (winter barley) TRZAS = Triticum aestivum (spring wheat) TRZAW = Triticum aestivum (winter wheat) TRZDU = Triticum aestivum (durum wheat) AVESA = Avena sativa (common oat)

Example 5

A safened composition comprising cloquintocet-triisopropanolamine salt (CQC-TIPA) and Compound A was tested on spring barley (HORVS) and spring wheat (TRZAS), and the phytotoxicity of the safened composition on each crop was measured. In addition, the efficacy of the safened compositions on undesirable vegetation, including wild chamomile (MATCH, Matricaria chamomilla), Russian thistle (SASKR, Salsola kali), and winter rape (BRSNW, Brassica napus), was measured.

The results are summarized in Table 10 below.

TABLE 10 Safening of Effects (% visual injury) of Cloquintocet- triisopropanolamine salt (CQC-TIPA) and Compound A on grain crops and weeds. Application Compound A 20 0 0 0 20 20 20 rate (g/ha) CQC-TIPA 0 10 20 40 10 20 40 Herbicide: 2:1 1:1 1:2 Safener Ratio HORVS Ob 0 0 0 0 0 0 0 Ex — — — — 0 0 0 Δ 0 0 0 TRZAS Ob 25 0 0 0 0 0 0 Ex — — — — 25 25 25 Δ −25 −25 −25 MATCH Ob 50 0 0 0 50 60 Ex — — — — 50 50 Δ 0 10 SASKR Ob 60 0 0 0 60 60 Ex — — — — 60 60 Δ 0 0 BRSNW Ob 95 0 0 0 90 95 Ex — — — — 95 95 Δ −5 0 g/ha = grams per hectare HORVS = Hordeum vulgare (spring barley) TRZAS = Triticum aestivum (spring wheat) MATCH = Matricaria chamomilla (wild chamomile) SASKR = Salsola kali (Russian thistle) BRSNW = Brassica napus (winter rape)

Example 6

A safened composition comprising cloquintocet-methyl (CQC-methyl) and Compound A was tested on spring barley (HORVS) and spring wheat (TRZAS), and the phytotoxicity of the safened composition on each crop was measured. In addition, the efficacy of the safened compositions on undesirable vegetation, including wild chamomile (MATCH, Matricaria chamomilla), Russian thistle (SASKR, Salsola kali), and winter rape (BRSNW, Brassica napus), was measured.

The results are summarized in Table 11 below.

TABLE 11 Safening of Effects (% visual injury) of Cloquintocet- methyl (CQC-methyl) and Compound A on grain crops and weeds. Application Compound A 20 0 0 0 20 20 20 rate (g/ha) CQC-methyl 0 10 20 40 10 20 40 Herbicide: 2:1 1:1 1:2 Safener Ratio HORVS Ob 0 0 0 0 0 0 0 Ex — — — — 0 0 0 Δ 0 0 0 TRZAS Ob 25 0 0 0 0 0 0 Ex — — — — 25 25 25 Δ −25 −25 −25 MATCH Ob 50 0 0 0 65 40 Ex — — — — 50 50 Δ 15 −10 SASKR Ob 60 0 0 0 60 50 Ex — — — — 60 60 Δ 0 −10 BRSNW Ob 95 0 0 0 85 80 Ex — — — — 95 95 Δ −10 −15 g/ha = grams per hectare HORVS = Hordeum vulgare (spring barley) TRZAS = Triticum aestivum (spring wheat) MATCH = Matricaria chamomilla (wild chamomile) SASKR = Salsola kali (Russian thistle) BRSNW = Brassica napus (winter rape)

Example 7

A safened composition comprising cloquintocet-mexyl (CQC-mexyl) and Compound B was tested on spring barley (HORVS), winter barley (HORVW), spring wheat (TRZAS), winter wheat (TRZAW), durum wheat (TRZDU), and common oats (AVESA), and the phytotoxicity of the safened composition on each crop was measured. In addition, the efficacy of the safened compositions on undesirable vegetation, including winter rape (BRSNW, Brassica napus), common buckwheat (FAGES, Fagopyrum esculentum), wild buckwheat (POLCO, Polygonum convulvus), Russian thistle (SASKR, Salsola kali), and wild mustard (SINAR, Sinapis arvensis), was measured.

The results are summarized in Tables 12-13 below.

TABLE 12 Safening of Effects (% visual injury) of Cloquintocet- mexyl (CQC-mexyl) and Compound B on grain crops. Application Compound B 40 0 40 rate (g/ha) CQC-mexyl 0 40 40 Herbicide: 1:1 Safener Ratio HORVS Ob 25 0 13 Ex — — 25 Δ −12 HORVW Ob 38 0 13 Ex — — 38 Δ 0 0 −25 TRZAS Ob 48 0 0 Ex — — 48 Δ −48 TRZAW Ob 50 0 10 Ex — — 50 Δ −40 TRZDU Ob 40 0 0 Ex — — 40 Δ −40 AVESA Ob 0 0 0 Ex — — 0 Δ 0 g/ha = grams per hectare HORVS = Hordeum vulgare (spring barley) HORVW = Hordeum vulgare (winter barley) TRZAS = Triticum aestivum (spring wheat) TRZAW = Triticum aestivum (winter wheat) TRZDU = Triticum aestivum (durum wheat) AVESA = Avena sativa (common oat)

TABLE 13 Safening of Effects (% visual injury) of Cloquintocet-mexyl (CQC-mexyl) and Compound B on grain crops and weeds. Appli- Compound 20 0 0 0 0 20 20 20 20 cation B rate CQC- 0 5 10 20 40 5 10 20 40 (g/ha) mexyl Herbicide: 4:1 2:1 1:1 1:2 Safener Ratio TRZAS Ob 28 0 0 0 0 20 15 10 0 Ex — — — — — 28 28 28 28 Δ −8 −13 −18 −28 HORVS Ob 30 0 0 0 0 23 8 15 10 Ex — — — — — 30 30 30 30 Δ −8 −23 −15 −20 BRSNW Ob 100 0 0 0 0 98 100 99 100 Ex — — — — — 100 100 100 100 Δ −3 0 −2 0 FAGES Ob 78 0 0 0 0 83 80 83 83 Ex — — — — — 78 78 78 78 Δ 5 3 5 5 POLCO Ob 100 0 0 0 0 100 100 100 100 Ex — — — — — 100 100 100 100 Δ 0 0 0 0 SASKR Ob 70 0 0 0 0 73 78 73 73 Ex — — — — — 70 70 70 70 Δ 3 8 3 3 SINAR Ob 80 0 0 0 0 75 80 83 75 Ex — — — — — 80 80 80 80 Δ −5 0 3 −5 g/ha = grams per hectare TRZAS = Triticum aestivum (spring wheat) HORVS = Hordeum vulgare (spring barley) BRSNW = Brassica napus (winter rape) FAGES = Fagopyrum esculentum (common buckwheat) POLCO = Polygonum convulvus (wild buckwheat) SASKR = Salsola kali (Russian thistle) SINAR = Sinapis arvensis (wild mustard)

Example 8

A safened composition comprising cloquintocet-mexyl (CQC-mexyl) and Compound A was tested on spring barley (HORVS), winter barley (HORVW), spring wheat (TRZAS), winter wheat (TRZAW), durum wheat (TRZDU), and common oats (AVESA), and the phytotoxicity of the safened composition on each crop was measured. In addition, the efficacy of the safened compositions on undesirable vegetation, including field chamomile (ANTAR, Anthemis arvensis), winter rape (BRSNW, Brassica napus), false chamomile (MATIN, Matricaria inodora), and wild mustard (SINAR, Sinapis arvensis), was measured.

The results are summarized in Tables 14-16 below.

TABLE 14 Safening of Effects (% visual injury) of Cloquintocet- mexyl (CQC-mexyl) and Compound A on grain crops. Application Compound A 40 0 40 rate (g/ha) CQC-mexyl 0 40 40 Herbicide: 1:1 Safener Ratio HORVS Ob 20 0 0 Ex — — 20 Δ −20 HORVW Ob 40 0 13 Ex — — 40 Δ 0 0 −28 TRZAS Ob 45 0 0 Ex — — 45 Δ −45 TRZAW Ob 35 0 8 Ex — — 35 Δ −28 TRZDU Ob 45 0 0 Ex — — 45 Δ −45 AVESA Ob 0 0 0 Ex — — 0 Δ 0 g/ha = grams per hectare HORVS = Hordeum vulgare (spring barley) HORVW = Hordeum vulgare (winter barley) TRZAS = Triticum aestivum (spring wheat) TRZAW = Triticum aestivum (winter wheat) TRZDU = Triticum aestivum (durum wheat) AVESA = Avena sativa (common oat)

TABLE 15 Safening of Effects (% visual injury) of Cloquintocet-mexyl (CQC-mexyl) and Compound A on grain crops and weeds. Appli- Compound 20 0 0 0 0 20 20 20 20 cation A rate CQC- 0 5 10 20 40 5 10 20 40 (g/ha) mexyl Herbicide: 4:1 2:1 1:1 1:2 Safener Ratio TRZAS Ob 15 0 0 0 0 0 0 0 0 Ex — — — — — 15 15 15 15 Δ −15 −15 −15 −15 TRZAW Ob 20 0 0 0 0 5 5 5 0 Ex — — — — — 20 20 20 20 Δ −15 −15 −15 −20 HORVS Ob 20 0 0 0 0 0 0 0 0 Ex — — — — — 20 20 20 20 Δ −20 −20 −20 −20 HORVW Ob 15 0 0 0 0 0 0 0 0 Ex — — — — — 15 15 15 15 Δ −15 −15 −15 −15 ANTAR Ob 95 0 0 0 0 99 95 100 100 Ex — — — — — 95 95 95 95 Δ 4 0 5 5 BRSNW Ob 70 0 0 0 0 70 65 75 75 Ex — — — — — 70 70 70 70 Δ 0 −5 5 5 g/ha = grams per hectare TRZAS = Triticum aestivum (spring wheat) TRZAW = Triticum aestivum (winter wheat) HORVS = Hordeum vulgare (spring barley) HORVW = Hordeum vulgare (winter barley) ANTAR = Anthemis arvensis (field chamomile) BRSNW = Brassica napus (winter rape)

TABLE 16 Safening of Effects (% visual injury) of Cloquintocet-mexyl (CQC-mexyl) and Compound A on grain crops and weeds. Appli- Com- 40 0 0 0 0 40 40 40 40 cation pound rate A (g/ha) CQC- 0 10 20 40 80 10 20 40 80 mexyl Herbicide: 4:1 2:1 1:1 1:2 Safener Ratio TRZAS Ob 40 0 0 0 0 0 0 0 0 Ex — — — — — 40 40 40 40 Δ −40 −40 −40 −40 TRZAW Ob 35 0 0 0 0 0 0 0 0 Ex — — — — — 35 35 35 35 Δ −35 −35 −35 −35 HORVS Ob 40 0 0 0 0 10 10 0 0 Ex — — — — — 40 40 40 40 Δ −30 −30 −40 −40 HORVW Ob 30 0 0 0 0 10 10 0 0 Ex — — — — — 30 30 30 30 Δ −20 −20 −30 −30 MATIN Ob 100 0 0 0 0 98 100 98 95 Ex — — — — — 100 100 100 100 Δ −3 0 −3 −5 SINAR Ob 99 0 0 0 0 100 100 97 99 Ex — — — — — 99 99 99 99 Δ 2 2 −2 0 g/ha = grams per hectare TRZAS = Triticum aestivum (spring wheat) TRZAW = Triticum aestivum (winter wheat) HORVS = Hordeum vulgare (spring barley) HORVW = Hordeum vulgare (winter barley) MATIN = Matricaria inodora (false chamomile) SINAR = Sinapis arvensis (wild mustard)

Example 9

A safened composition comprising cloquintocet-mexyl (CQC-mexyl) and Compound A was tested on maize (ZEAMX), and the phytotoxicity of the safened composition on the crop was measured. In addition, the efficacy of the safened compositions on undesirable vegetation, including pigweed (AMARE, Amaranthus retroflexus), nutsedge (CYPES, Cyperus esculentus), and common sunflower (HELAN, Helianthus annuus), was measured.

The results are summarized in Table 17 below.

TABLE 17 Safening of Effects (% visual injury) of Cloquintocet-mexyl (CQC-mexyl) and Compound A on maize and weeds. Appli- Com- 40 0 0 0 0 40 40 40 40 cation pound rate (g/ha) A CQC- 0 20 40 80 120 20 40 80 120 mexyl Herbicide: 2:1 1:1 1:2 1:3 Safener Ratio ZEAMX Ob 55 0 0 0 0 15 8 5 0 Ex — — — — — 55 55 55 55 Δ −40 −48 −50 −55 AMARE Ob 100 0 0 0 0 100 100 98 94 Ex — — — — — 100 100 100 100 Δ 0 0 −3 −7 CYPES Ob 73 0 0 0 0 55 58 75 65 Ex — — — — — 73 73 73 73 Δ −18 −15 3 −8 HELAN Ob 100 0 0 0 0 100 100 100 100 Ex — — — — — 100 100 100 100 Δ 0 0 0 0 g/ha = grams per hectare ZEAMX = Zea mays (maize) AMARE = Amaranthus retroflexus (pigweed) CYPES = Cyperus esculentus (nutsedge) HELAN = Helianthus annuus (common sunflower)

Example 10

A safened composition comprising cloquintocet-acid (CQC-a) and Compound A was tested on maize (ZEAMX), and the phytotoxicity of the safened composition on the crop was measured. In addition, the efficacy of the safened compositions on undesirable vegetation, including pigweed (AMARE, Amaranthus retroflexus), nutsedge (CYPES, Cyperus esculentus), and common sunflower (HELAN, Helianthus annuus), was measured.

The results are summarized in Table 18 below.

TABLE 18 Safening of Effects (% visual injury) of Cloquintocet-acid (CQC-a) and Compound A on maize and weeds. Appli- Compound 40 0 0 0 0 40 40 40 40 cation A rate (g/ha) CQC-a 0 20 40 80 120 20 40 80 120 Herbicide: 2:1 1:1 1:2 1:3 Safener Ratio ZEAMX Ob 55 0 0 0 0 15 10 8 8 Ex — — — — — 55 55 55 55 Δ -40 -45 -48 -48 AMARE Ob 100 0 0 0 0 93 100 100 99 Ex — — — — — 100 100 100 100 Δ -8 0 0 -1 CYPES Ob 73 0 0 0 0 65 88 73 90 Ex — — — — — 73 73 73 73 Δ -8 15 0 18 HELAN Ob 100 0 0 0 0 100 100 100 100 Ex — — — — — 100 100 100 100 Δ 0 0 0 0 g/ha = grams per hectare ZEAMX = Zea mays (maize) AMARE = Amaranthus retroflexus (pigweed) CYPES = Cyperus esculentus (nutsedge) HELAN = Helianthus annuus (common sunflower)

Example 11

A safened composition comprising cloquintocet-mexyl (CQC-mexyl) and Compound A was tested on winter wheat (TRZAW), rice (ORYSA), and maize (ZEAMX), and the phytotoxicity of the safened composition on the crop was measured. In addition, the efficacy of the safened compositions on undesirable vegetation, including velvetleaf (ABUTH, Abutilon theophrasti), blackgrass (ALOMY, Alopecurus myosuroides), pigweed (AMARE, Amaranthus retroflexus), wild oat (AVEFA, Avena fatua), winter rape (BRSNW, Brassica napus), common lambsquarters (CHEAL, Chenopodium album L.), Canada thistle (CIRAR, Cirsium arvense), nutsedge (CYPES, Cyperus esculentus), large crabgrass (DIGSA, Digitaria sanguinalis), barnyardgrass (ECHCG, Echinochloa crus-galli), Canada horseweed (ERICA, Erigeron canadensis), soybean (GLXMA, Glycine max), common sunflower (HELAN, Helianthus annuus), ivyleaf morningglory (IPOHE, Ipomoea hederacea), kochia (KCHSC, Kochia scoparia), Chinese sprangletop (LEFCH, Leptochloa chinensis), Italian ryegrass (LOLMU, Lolium multiflorum), wild buckwheat (POLCO, Polygonum convolvulus), giant foxtail (SETFA, Setaria faberi), Johnson grass (SORHA, Sorghum halepense), and wild pansy (VIOTR, Viola tricolor) was measured.

The results are summarized in Table 19 below.

TABLE 19 Safening of Effects (% visual injury) of Cloquintocet-mexyl (CQC- mexyl) and Compound A on maize and weeds. Application Compound A 20 0 0 0 20 20 20 rate (g/ha) CQC-mexyl 0 20 40 80 20 40 80 Herbicide: 1:1 1:2 1:4 Safener Ratio TRZAW Ob 25 0 0 0 0 0 0 Ex — — — — 25 25 25 Δ −25 −25 −25 ORYSA Ob 10 0 0 0 5 20 10 Ex — — — — 10 10 10 Δ −5 10 0 ZEAMX Ob 13 0 0 0 0 5 5 Ex — — — — 13 13 13 Δ −13 −8 −8 ABUTH Ob 95 0 0 0 93 95 95 Ex — — — — 95 95 95 Δ −2 0 0 ALOMY Ob 0 0 0 0 0 0 0 Ex — — — — 0 0 0 Δ 0 0 0 AMARE Ob 93 0 0 0 100 100 100 Ex — — — — 93 93 93 Δ 7 7 7 AVEFA Ob 0 0 0 0 0 0 0 Ex — — — — 0 0 0 Δ 0 0 0 BRSNW Ob 85 0 0 0 90 90 80 Ex — — — — 85 85 85 Δ 5 5 −5 CHEAL Ob 88 0 0 0 100 100 100 Ex — — — — 88 88 88 Δ 12 12 12 CIRAR Ob 95 0 0 0 70 70 100 Ex — — — — 95 95 95 Δ −25 −25 5 CYPES Ob 30 0 0 0 30 30 10 Ex — — — — 30 30 30 Δ 0 0 −20 DIGSA Ob 30 0 0 0 40 40 40 Ex — — — — 30 30 30 Δ 10 10 10 ECHCG Ob 85 0 0 0 90 80 85 Ex — — — — 85 85 85 Δ 5 −5 0 ERICA Ob 95 0 0 0 97 97 95 Ex — — — — 95 95 95 Δ 2 2 0 GLXMA Ob 100 0 0 0 100 100 100 Ex — — — — 100 100 100 Δ 0 0 0 HELAN Ob 95 0 0 0 100 100 100 Ex — — — — 95 95 95 Δ 5 5 5 IPOHE Ob 0 0 0 0 0 0 0 Ex — — — — 0 0 0 Δ 0 0 0 KCHSC Ob 97 0 0 0 97 97 95 Ex — — — — 97 97 97 Δ 0 0 −2 LEFCH Ob 60 0 0 0 20 10 50 Ex — — — — 60 60 60 Δ −40 −50 −10 LOLMU Ob 5 0 0 0 5 5 5 Ex — — — — 5 5 5 Δ 0 0 0 POLCO Ob 100 0 0 0 100 100 100 Ex — — — — 100 100 100 Δ 0 0 0 SETFA Ob 65 0 0 0 95 70 75 Ex — — — — 65 65 65 Δ 30 5 10 SORHA Ob 0 0 0 0 0 0 0 Ex — — — — 0 0 0 Δ 0 0 0 VIOTR Ob 30 0 0 0 10 5 5 Ex — — — — 30 30 30 Δ −20 −25 −25 g/ha = grams per hectare TRZAW = Triticum aestivum (winter wheat) ORYSA = Oryza sativa (common rice) ZEAMX = Zea mays (maize) ABUTH = Abutilon theophrasti (velvetleaf) ALOMY = Alopecurus myosuroides (blackgrass) AMARE = Amaranthus retroflexus (pigweed) AVEFA = Avena fatua (wild oat) BRSNW = Brassica napus (winter rape) CHEAL = Chenopodium album L. (common lambsquarters) CIRAR = Cirsium arvense (Canada thistle) CYPES = Cyperus esculentus (nutsedge) DIGSA = Digitaria sanguinalis (large crabgrass) ECHCG = Echinochloa crus-galli (barnyardgrass) ERICA = Erigeron canadensis (Canada horseweed) GLXMA = Glycine max (soybean) HELAN = Helianthus annuus (common sunflower) IPOHE = Ipomoea hederacea (ivyleaf morningglory) KCHSC = Kochia scoparia (kochia) LEFCH = Leptochloa chinensis (Chinese sprangletop) LOLMU = Lolium multiflorum (Italian ryegrass) POLCO = Polygonum convolvulus (wild buckwheat) SETFA = Setaria faberi (giant foxtail) SORHA = Sorghum halepense (Johnson grass) VIOTR = Viola tricolor (wild pansy)

The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative compositions and method steps disclosed herein are specifically described, other combinations of the compositions and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein; however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated. The term “comprising” and variations thereof as used herein is used synonymously with the term “including” and variations thereof and are open, non-limiting terms. Although the terms “comprising” and “including” have been used herein to describe various aspects, the terms “consisting essentially of” and “consisting of” can be used in place of “comprising” and “including” to provide for more specific aspects and are also disclosed. Other than in the examples, or where otherwise noted, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood to be construed in light of the number of significant digits and ordinary rounding approaches, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims. 

1. A safened composition, comprising: (a) a pyridine carboxylate herbicide defined by Formula (I): wherein:

R¹ is cyanomethyl or propargyl; R² and R^(2′) are independently hydrogen, C₁-C₆ alkyl, formyl, alkoxycarbonyl, or acyl; R³, R^(3′), R^(3″), and R^(3′″) are independently hydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₃ alkoxy, or C₁-C₃ haloalkoxy; or an agriculturally acceptable N-oxide, salt, or ester thereof; and (b) a safener comprising cloquintocet or an agriculturally acceptable salt or ester thereof.
 2. The composition of claim 1, wherein the pyridine carboxylate herbicide compound is cyanomethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate:


3. The composition of claim 1, wherein the pyridine carboxylate herbicide compound is propargyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate:


4. The composition of claim 1, wherein the safener comprises an agriculturally acceptable ester of cloquintocet.
 5. The composition of claim 4, wherein the agriculturally acceptable ester of cloquintocet is selected from the group consisting of methyl, ethyl, and mexyl esters of cloquintocet, and combinations thereof.
 6. The composition of claim 1, wherein the safener comprises an agriculturally acceptable salt of cloquintocet.
 7. The composition of claim 6, wherein the agriculturally acceptable salt of cloquintocet is selected from the group consisting of sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, monoisopropanolammonium, diisopropanolammonium, triisopropanolammonium, choline, N,N-dimethylethanolammonium, diethylammonium, dimethylammonium, trimethylammonium, triethylammonium, and isopropylammonium salts of cloquintocet, and combinations thereof.
 8. The composition of claim 1, wherein the weight ratio of the pyridine carboxylate herbicide (in g ae/ha) to the safener (in g ai/ha) is from about 1:5 to about 65:1.
 9. The composition of claim 1, further comprising an additional pesticide.
 10. The composition of claim 1, wherein the composition does not include a herbicidal active ingredient in addition to (a).
 11. A method of controlling undesirable vegetation in a crop, comprising applying to vegetation or an area adjacent the vegetation or applying to soil or water to limit the emergence or growth of vegetation a safened composition, comprising: (a) (a) a pyridine carboxylate herbicide defined by Formula (I):

wherein R¹ is cyanomethyl or propargyl; R² and R^(2′) are independently hydrogen, C₁-C₆ alkyl, formyl, alkoxycarbonyl, or acyl; R³, R^(3′), R^(3″), and R^(3′″) are independently hydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₃ alkoxy, or C₁-C₃ haloalkoxy; or an agriculturally acceptable N-oxide, salt, or ester thereof; and (b) a safener comprising cloquintocet or an agriculturally acceptable salt or ester thereof; wherein the herbicide is applied in an amount of at least 1 g ae/ha; and wherein the safener is applied in an amount of at least 1 g ai/ha.
 12. The method of claim 11, wherein the pyridine carboxylate herbicide compound is cyanomethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate:


13. The method of claim 11, wherein the pyridine carboxylate herbicide compound is propargyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate:


14. The method of claim 11, wherein the herbicide and the safener are applied simultaneously.
 15. The method of claim 11, wherein the safener comprises an agriculturally acceptable ester of cloquintocet.
 16. The method of claim 15, wherein the agriculturally acceptable ester of cloquintocet is selected from the group consisting of methyl, ethyl, and mexyl esters of cloquintocet, and combinations thereof.
 17. The method of claim 11, wherein the safener comprises an agriculturally acceptable salt of cloquintocet.
 18. The method of claim 15, wherein the agriculturally acceptable salt of cloquintocet is selected from the group consisting of sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, monoisopropanolammonium, diisopropanolammonium, triisopropanolammonium, choline, N,N-dimethylethanolammonium, diethylammonium, dimethylammonium, trimethylammonium, triethylammonium, and isopropylammonium salts of cloquintocet, and combinations thereof.
 19. The method of claim 11, wherein the herbicide is provided in amount of 1 g ae/ha to 300 g ae/ha.
 20. The method of claim 11, wherein weight ratio of the pyridine carboxylate herbicide (in g ae/ha) to the safener (in g ai/ha) is from about 1:5 to about 65:1.
 21. The method of claim 11, wherein the pyridine carboxylate herbicide is applied pre-emergently or post-emergently to the undesirable vegetation and the safener is applied as a seed treatment to the crop.
 22. The method of claim 11, further comprising applying an additional pesticide.
 23. The method of claim 11, wherein the composition does not include a herbicidal active ingredient in addition to (a). 